Branched organosilicon compound, method of preparing same, and copolymer formed therewith

ABSTRACT

A branched organosilicon compound (“compound”) having the general formula (R1)3Si—X—Y is provided. In the formula: each R1 is selected from R and —OSi(R4)3, with the proviso that at least one R1 is —OSi(R4)3; each R is independently a substituted or unsubstituted hydrocarbyl group; each R4 is selected from R, —OSi(R5)3, and —[OSiR2]mOSiR3; each R5 is selected from R, —OSi(R6)3, and —[OSiR2]mOSiR3; each R6 is selected from R and —[OSiR2]mOSiR3; with the proviso that at least one of R4, R5 and R6 is —[OSiR2]mOSiR3; 0&lt;m≤100; X is a divalent linking group; and Y is selected from one of formulas (1)-(111) described herein. Also provided is a method of preparing the compound via hydrosilylation reaction, a copolymer comprising the reaction product of the compound and a second compound reactive with the compound, a method of forming the copolymer, and a composition including at least one of the compound and the copolymer.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to and all advantages of U.S.Provisional Patent Application No. 62/786,703 filed on 31 Dec. 2018, thecontent of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention generally relates to organosilicon compounds and,more specifically, to a branched organosilicon compound, a copolymerformed therewith, methods of preparing the same, and compositionscomprising the same.

DESCRIPTION OF THE RELATED ART

Silicones are polymeric materials used in numerous commercialapplications, primarily due to significant advantages they possess overtheir carbon-based analogues. More precisely called polymerizedsiloxanes or polysiloxanes, silicones have an inorganic silicon-oxygenbackbone chain (•••—Si—O—Si—O—Si—O—•••) with organic side groupsattached to the silicon atoms.

Organic side groups may be used to link two or more of these backbonestogether. By varying the —Si—O— chain lengths, side groups, andcrosslinking, silicones can be synthesized with a wide variety ofproperties and compositions. They can vary in consistency from liquid togel to rubber to hard plastic. The most common siloxane is linearpolydimethylsiloxane (PDMS), a silicone oil. The second largest group ofsilicone materials is based on silicone resins, which are formed bybranched and cage-like oligosiloxanes.

Another group of silicone materials are silicone dendrimers. Dendrimersare polymers that have a highly branched structure which extendsradially from a single core. A dendrimer is a repetitively branchedmolecule, typically symmetric (or near symmetric) around the core, andoften adopts a spherical or ellipsoidal three-dimensional morphology.Dendritic polymers can also be described as tree-like macromoleculesconsisting of unique branch-upon-branch-upon-branch structuralorganizations or generations.

Dendritic silicones or macromolecules have molecular shapes, sizes, andfunctionality that provide for many potential end applications. Thus,there remains an opportunity to provide improved branched compoundsbased on silicon, as well as improved methods of forming such compounds.There also remains an opportunity to provide improved copolymers andimproved compositions based on or having such compounds.

BRIEF SUMMARY OF THE INVENTION

A branched organosilicon compound is provided. The branchedorganosilicon compound has the general formula:

where each R¹ is selected from R and —OSi(R⁴)₃, with the proviso that atleast one R¹ is —OSi(R⁴)₃; where each R⁴ is selected from R, —OSi(R⁵)₃,and —[OSiR₂]mOSiR₃, where 0≤m≤100; where each R⁵ is selected from R,—OSi(R⁶)₃, and —[OSiR₂]mOSiR₃, where m is defined above; where each R⁶is selected from R and —[OSiR₂]mOSiR₃, where m is defined above; withthe proviso that at least one of R⁴, R⁵ and R⁶ is —[OSiR₂]mOSiR₃, wherem is defined above; X is a divalent linking group; and Y is selectedfrom one of formulas (I)-(III):

where each R is an independently selected substituted or unsubstitutedhydrocarbyl group; each D¹ is an independently selected divalenthydrocarbon group; each subscript a is independently 0 or 1; eachsubscript b is independently 0 or 1; each subscript e is independently 1or 2; each subscript f is independently 0 or 1, with the proviso thatwhen f is 1, b is 1; subscript t is ≥0; subscript u is >0; 0≤n≤10; andR³ comprises a halogen atom, an acryloxy functional moiety, analkoxysilyl functional moiety, or an epoxy functional moiety.

A method of preparing the branched organosilicon compound is alsoprovided. The method includes reacting an organosilicon compound and afunctional compound in the presence of a hydrosilylation catalyst togive the branched organosilicon compound. The organosilicon compoundincludes one of a silicon-bonded hydrogen atom and a silicon-bondedethylenically unsaturated group, with the proviso that when theorganosilicon compound includes a silicon-bonded hydrogen atom, thefunctional compound includes an ethylenically unsaturated group, andwhen the organosilicon compound includes a silicon-bonded ethylenicallyunsaturated group. The functional compound includes a silicon-bondedhydrogen atom.

A copolymer is also provided. The copolymer comprises the reactionproduct of the branched organosilicon compound and a second compoundreactive with the branched organosilicon compound.

A method of preparing the copolymer is further provided, and includesreacting the branched organosilicon compound and the second compoundreactive with the branched organosilicon compound to give the copolymer.

A composition is also provided. The composition includes at least one ofthe branched organosilicon compound and the copolymer.

DETAILED DESCRIPTION OF THE INVENTION

A branched organosilicon compound has the general formula:

where each R¹ is selected from R and —OSi(R⁴)₃, with the proviso that atleast one R¹ is —OSi(R⁴)₃; where each R⁴ is selected from R, —OSi(R⁵)₃,and —[OSiR₂]_(m)OSiR₃, where 0≤m≤100; where each R⁵ is selected from R,—OSi(R⁶)₃, and —[OSiR₂]_(m)OSiR₃, where m is defined above; where eachR⁶ is selected from R and —[OSiR₂]_(m)OSiR₃, where m is defined above;with the proviso that at least one of R⁴, R⁵ and R⁶ is—[OSiR₂]_(m)OSiR₃, where m is defined above X is a divalent linkinggroup; and Y is selected from one of formulas (I)-(III):

where each R is an independently selected substituted or unsubstitutedhydrocarbyl group; each D¹ is an independently selected divalenthydrocarbon group; each subscript a is independently 0 or 1; eachsubscript b is independently 0 or 1; each subscript e is independently 1or 2; each subscript f is independently 0 or 1, with the proviso thatwhen f is 1, b is 1; subscript t is ≥0; subscript u is >0; 0≤n≤10; andR³ comprises a halogen atom, an acryloxy functional moiety, analkoxysilyl functional moiety, or an epoxy functional moiety.

Each R is independently selected and may be linear, branched, cyclic, orcombinations thereof. Cyclic hydrocarbyl groups encompass aryl groups aswell as saturated or non-conjugated cyclic groups. Cyclic hydrocarbylgroups may be monocyclic or polycyclic. Linear and branched hydrocarbylgroups may independently be saturated or unsaturated. One example of acombination of a linear and cyclic hydrocarbyl group is an aralkylgroup. By “substituted,” it is meant that one or more hydrogen atoms maybe replaced with atoms other than hydrogen (e.g. a halogen atom, such aschlorine, fluorine, bromine, etc.), or a carbon atom within the chain ofR may be replaced with an atom other than carbon, i.e., R may includeone or more heteroatoms within the chain, such as oxygen, sulfur,nitrogen, etc. Suitable alkyl groups are exemplified by, but not limitedto, methyl, ethyl, propyl (e.g., iso-propyl and/or n-propyl), butyl(e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl (e.g.,isopentyl, neopentyl, and/or tert-pentyl), hexyl, as well as branchedsaturated hydrocarbon groups of 6 carbon atoms. Suitable aryl groups areexemplified by, but not limited to, phenyl, tolyl, xylyl, naphthyl,benzyl, and dimethyl phenyl. Suitable alkenyl groups include vinyl,allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl,hexenyl, and cyclohexenyl groups. Suitable monovalent halogenatedhydrocarbon groups include, but are not limited to, a halogenated alkylgroup of 1 to 6 carbon atoms, or a halogenated aryl group of 6 to 10carbon atoms. Suitable halogenated alkyl groups are exemplified by, butnot limited to, the alkyl groups described above where one or morehydrogen atoms is replaced with a halogen atom, such as F or Cl. Forexample, fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl,4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl,5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl,2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl,2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl are examples ofsuitable halogenated alkyl groups. Suitable halogenated aryl groups areexemplified by, but not limited to, the aryl groups described abovewhere one or more hydrogen atoms is replaced with a halogen atom, suchas F or Cl. For example, chlorobenzyl and fluorobenzyl are suitablehalogenated aryl groups.

In specific embodiments, each R is independently an alkyl group havingfrom 1 to 10, alternatively from 1 to 8, alternatively from 1 to 6,alternatively from 1 to 4, alternatively from 1 to 3, alternatively from1 to 2, alternatively 1, carbon atom(s).

Each R¹ is selected from R and —OSi(R⁴)₃, with the proviso that at leastone R¹ is —OSi(R⁴)₃. In certain embodiments, at least two of R¹ are—OSi(R⁴)₃. In specific embodiments, all three of R¹ are —OSi(R⁴)₃. Whena greater number of R¹ are —OSi(R⁴)₃, the organosilicon compound has agreater level of branching. For example, when each R¹ is —OSi(R⁴)₃ andthe Si—X bond is a silicon-carbon bond, the silicon atom to which eachR¹ is bonded is a T siloxy unit. Alternatively, when two of R¹ are—OSi(R⁴)₃ and the Si—X bond is a silicon-carbon bond, the silicon atomto which each R¹ is bonded is a D siloxy unit.

Each R⁴ is selected from R, —OSi(R⁵)₃, and —[OSiR₂]_(m)OSiR₃, where0≤m≤100. Depending on a selection of R⁴ and R⁵, further branching can bepresent in the branched organosilicon compound. For example, when eachR⁴ is R, then each —OSi(R⁴)₃ moiety is a terminal M siloxy unit. Saiddifferently, when each R¹ is —OSi(R⁴)₃, and when each R⁴ is R, then eachR¹ can be written as OSiR₃, and each R¹ is an M siloxy unit. In suchembodiments, the branched organosilicon compound includes a T siloxyunit (to which X is bonded) capped by three M siloxy units. When R⁴ is—[OSiR₂]_(m)OSiR₃, R⁴ includes optional D siloxy units (i.e., thosesiloxy units in the moiety indicated by subscript m), and an M siloxyunit (represented by OSiR₃). Thus, for example, when each R¹ is—OSi(R⁴)₃, and when each R⁴ is —[OSiR₂]_(m)OSiR₃, then each R¹ includesa Q siloxy unit. In such embodiments, each R¹ is of formula—OSi([OSiR₂]_(m)OSiR₃)₃. When each m is 0, each R¹ is a Q siloxy unitendcapped with three M siloxy units. When m is greater than 0, each R¹includes a linear moiety with a degree of polymerization beingattributable to m. This linear moiety, if present, is generally adiorganosiloxane moiety.

Subscript m is from (and including) 0 to 100, alternatively from 0 to80, alternatively from 0 to 60, alternatively from 0 to 40,alternatively from 0 to 20, alternatively from 0 to 19, alternativelyfrom 0 to 18, alternatively from 0 to 17, alternatively from 0 to 16,alternatively from 0 to 15, alternatively from 0 to 14, alternativelyfrom 0 to 13, alternatively from 0 to 12, alternatively from 0 to 11,alternatively from 0 to 10, alternatively from 0 to 9, alternativelyfrom 0 to 8, alternatively from 0 to 7, alternatively from 0 to 6,alternatively from 0 to 5, alternatively from 0 to 4, alternatively from0 to 3, alternatively from 0 to 2, alternatively from 0 to 1,alternatively is 0. Typically, each subscript m is 0 such that thebranched moiety of the branched organosilicon compound is free from Dsiloxy units.

As set forth above, each R⁴ can also be —OSi(R⁵)₃. In such embodiments,depending a selection of R⁵, further branching can be present in thebranched organosilicon compound. Each R⁵ is selected from R, —OSi(R⁶)₃,and —[OSiR₂]_(m)OSiR₃, where m is defined above; where each R⁶ isselected from R and —[OSiR₂]_(m)OSiR₃, where m is defined above. Atleast one of R⁴, R⁵ and R⁶ is —[OSiR₂]_(m)OSiR₃, where m is definedabove. When R¹ is of formula —OSi(R⁴)₃, and when R⁴ is of formula—OSi(R⁵)₃, further siloxane bonds and branching is present in thebranched organosilicon compound. This is further the case when R⁵ is—OSi(R⁶)₃

In particular, each subsequent R moiety in the branched organosiliconcompound can impart a further generation of branching. For example, R¹can be of formula —OSi(R⁴)₃, R⁴ can be of formula —OSi(R⁵)₃, and R⁵ canbe —OSi(R⁶)₃. Thus, depending on a selection of each substituent,further branching attributable to T and/or Q siloxy units may be presentin the branched organosilicon compound.

Importantly, each of R, R¹, R⁴, R⁵, and R⁶ are independently selected.As such, the descriptions above relating to each of these substituentsis not meant to mean or imply that each substituent is the same. Anydescription above relating to R¹ may relate to only one R¹ or any numberof R¹ in the branched organosilicon compound, and so on.

In addition, different selections of R, R¹, R⁴, R⁵, and R⁶ can result inthe same structures. For example, if R¹ is —OSi(R⁴)₃, and if each R⁴ is—OSi(R⁵)₃, and if each R⁵ is R, then R¹ can be written as —OSi(—OSiR₃)₃.Similarly, if R¹ is —OSi(R⁴)₃, and if each R⁴ is —[OSiR₂]_(m)OSiR₃,where m is 0, then R¹ can be written as —OSi(—OSiR₃)₃. This results inthe same structure for R¹ based on different selections for R⁴. To thatend, at least one of R⁴, R⁵ and R⁶ is —[OSiR₂]_(m)OSiR₃. However, when mis 0, this proviso can be inherently met through alternative selections.For example, as noted above, if each R⁴ is —OSi(R⁵)₃, and if each R⁵ isR, then R¹ can be written as —OSi(—OSiR₃)₃, which is the same as if R¹is —OSi(R⁴)₃, and if each R⁴ is —[OSiR₂]_(m)OSiR₃, where m is 0. Itshall be considered that the proviso is met even if alternativeselections can result in the same structures as required in the proviso.

In certain embodiments, each R¹ is —OSi(R⁴)₃. In specific embodiments inwhich each R¹ is —OSi(R⁴)₃, at least one R⁴ is —[OSiR₂]_(m)OSiR₃, wherem is 0. Because m is 0, the at least one R⁴ is —OSiR₃. This is the samestructure as if at least one R⁴ is —OSi(R⁵)₃, and if each R⁵ is R. Bothselections result in at least one R⁴ being —OSiR₃. Thus, if at least oneR⁴ is —OSi(R⁵)₃, and if each R⁵ is R, it shall also be considered thatat least one of R⁴ is —[OSiR₂]_(m)OSiR₃, where m is 0.

The same is true for further generations of branching in the branchedorganosilicon compound. For example, just as different selectionsassociated with R⁴ and R⁵ can result in the same structure above,different selections for R⁵ and R⁶ can similarly result in the samestructure.

In certain embodiments, each R¹ is —OSi(R⁴)₃. In specific embodiments inwhich each R¹ is —OSi(R⁴)₃, one R⁴ is R in each —OSi(R⁴)₃ such that eachR¹ is —OSiR(R⁴)₂. In further specific embodiments, two R⁴ in —OSiR(R⁴)₂are each —OSi(R⁵)₃ moieties such that the branched organosiliconcompound has the following structure:

where R is independently selected and defined above, and each R⁵ isindependently selected and defined above, and X and Y are defined above.In certain embodiments, each R⁵ is R, and each R is methyl.

As noted above, the same structure of the branched organosiliconcompound can result from different selections. For example, the samebranched organosilicon compound as exemplified above results with thefollowing selections: each R¹ is —OSi(R⁴)₃, where one R⁴ is R and two ofR⁴ are —[OSiR₂]_(m)OSiR₃, where m is 0. Thus, in the structureexemplified above, the proviso that at least one of R⁴, R⁵ and R⁶ be—[OSiR₂]_(m)OSiR₃ is met regardless of the selections of R⁴ and R⁵utilized to arrive at the resulting structure.

In other embodiments, one R¹ is R, and two of R¹ are —OSi(R⁴)₃. Inspecific embodiments in which two of R¹ is —OSi(R⁴)₃, one R⁴ is R ineach —OSi(R⁴)₃ such that two of R¹ are —OSiR(R⁴)₂. In further specificembodiments, each R⁴ in —OSiR(R⁴)₂ is —OSi(R⁵)₃ such that the branchedorganosilicon compound has the following structure:

where R is independently selected and defined above, and each R⁵ isindependently selected and defined above, and X and Y are defined above.In certain embodiments, each R⁵ is R, and each R is methyl.

As noted above, the same structure of the branched organosiliconcompound can result from different selections. For example, the samebranched organosilicon compound as exemplified above results with thefollowing selections: one R¹ is R; two of R¹ are —OSi(R⁴)₃, where one R⁴is R and two of R⁴ are —[OSiR₂]_(m)OSiR₃, where m is 0, in each—OSi(R⁴)₃. Thus, in the structure exemplified above, the proviso that atleast one of R⁴, R⁵ and R⁶ be —[OSiR₂]_(m)OSiR₃ is met regardless of theselections of R⁴ and R⁵ utilized to arrive at the resulting structure.

In yet other embodiments, two of R¹ are R, and one R¹ is —OSi(R⁴)₃. Inspecific embodiments in which one of R¹ is —OSi(R⁴)₃, and one R⁴ is R in—OSi(R⁴)₃ such that this specific R¹ is —OSiR(R⁴)₂. In further specificembodiments, each R⁴ in —OSiR(R⁴)₂ is —OSi(R⁵)₃ such that the branchedorganosilicon compound has the following structure:

where R is independently selected and defined above, and each R⁵ isindependently selected and defined above, and X and Y are defined above.In certain embodiments, each R⁵ is R, and each R is methyl.

As noted above, the same structure of the branched organosiliconcompound can result from different selections. For example, the samebranched organosilicon compound as exemplified above results with thefollowing selections: two of R¹ are R; one of R¹ is —OSi(R⁴)₃, where oneR⁴ is R and two of R⁴ are —[OSiR₂]_(m)OSiR₃, where m is 0, in —OSi(R⁴)₃.Thus, in the structure exemplified above, the proviso that at least oneof R⁴, R⁵ and R⁶ be —[OSiR₂]_(m)OSiR₃ is met regardless of theselections of R⁴ and R⁵ utilized to arrive at the resulting structure.

In the exemplary structures set forth above, each R⁵ is R, and each R ismethyl. However, further generational branching can be introduced intothe branched organosilicon compound when R⁵ is other than R, i.e., whenR⁵ is selected from OSi(R⁶)₃, and —[OSiR₂]_(m)OSiR₃, where m is definedabove; where each R⁶ is selected from R and —[OSiR₂]_(m)OSiR₃, where mis defined above.

As set forth above, X is a divalent linking group. X is generally afunction of the mechanism utilized to prepare the branched organosiliconcompound. I certain embodiments, e.g. when the branched organosiliconcompound is prepared via hydrosilylation, X is a divalent hydrocarbongroup. When X is a divalent hydrocarbon group, X typically has from 2 to18 carbon atoms, and may include substitution and/or heteroatomstherein/on. For example, X can include one or more oxygen heteroatomssuch that X comprises an ether moiety. Alternatively, X can merelycomprise a pure hydrocarbon.

Y is selected from one of formulas (I)-(III), which are set forth above.In certain embodiments, Y has formula (I). In other embodiments, Y hasformula (II). In yet other embodiments, Y has formula (III).

In formulas (I) and (II), each subscript a is independently from 0 to 2,alternatively from 0 to 1. Typically, subscript a is 0. In someembodiments, each subscript a is 0.

With regard formula (I), each subscript b is independently 0 or 1. Insome embodiments, each subscript b is 0. In other embodiments, eachsubscript b is 1. Each subscript e is independently 1 or 2. In someembodiments, each subscript e is 1. In other embodiments, each subscripte is 2. Each subscript f is independently 0 or 1, with the proviso thatwhen f is 1, b is 1.

In some embodiments, each subscript f is 0. In other embodiments, eachsubscript f is 1, and thus each b is 1.

With regard to formula (II), subscript t is ≥0. In certain embodiments,subscript t is from 1 to 100, such as from 0 to 80, alternatively from 0to 60, alternatively from 0 to 30, alternatively from 0 to 10,alternatively from 0 to 5. Subscript u is >0. In particular embodiments,subscript u is from 1 to 20, such as from 1 to 15, alternatively from 1to 10, alternatively from 1 to 7, alternatively from 1 to 5, andalternatively from 1 to 3.

Each D¹ is an independently selected divalent hydrocarbon group havingfrom 2 to 18 carbon atoms, alternatively from 2 to 16 carbon atoms,alternatively from 2 to 14 carbon atoms, alternatively from 2 to 12carbon atoms, alternatively from 2 to 10 carbon atoms, alternativelyfrom 2 to 8 carbon atoms, alternatively from 2 to 6 carbon atoms,alternatively from 2 to 4 carbon atoms, alternatively 2 or 3 carbonatoms, alternatively 2 carbon atoms. Each D¹ may independently be linearor branched. For example, when D¹ has two carbon atoms, D¹ has formulaC₂H₄, and may be linear (CH₂CH₂) or branched (CHCH₃). In certainembodiments, D¹ is linear. In specific embodiments, each D¹ is C₂H₄.

With regard to formula (III), R³ comprises a halogen atom, an acryloxyfunctional moiety, an alkoxysilyl functional moiety, or an epoxyfunctional moiety. Because R³ comprises one of these atoms or moieties,R³ can optionally include a divalent linking group between the siliconatom to which R³ is bonded. The optional divalent linking group betweenthe silicon atom and the halogen atom, the acryloxy functional moiety,the alkoxysilyl functional moiety, or the epoxy functional moiety of R³can be a substituted and unsubstituted hydrocarbon group, an ethergroup, a siloxane group, a silyl group, or a combination thereof.

In certain embodiments, R³ comprises a halogen atom. The halogen atom isselected from fluorine (F), chlorine (Cl), bromine (Br), iodine (I), andastatine (At), alternatively from chlorine and bromine, alternativelychlorine. In specific embodiments, R³ is a halogen atom. In suchembodiments, the halogen atom is a silicon-bonded halogen atom and R³does not include any divalent linking group. Alternatively, R³ couldcomprise, for example, an alkyl chloride, where the alkyl group is thedivalent linking group. When R³ is a halogen atom, R³ can be ahydrolysable group, as silicon-bonded halogen atoms are hydrolysable.

In other embodiments, R³ comprises an acryloxy group of the formula:

where R⁸ is independently selected from hydrocarbyl groups and H. Insome such embodiments, R⁸ is H or —CH₃. When R³ comprises the acryloxygroup, R³ typically includes a divalent hydrocarbon group between theoxygen heteroatom of the acryloxy group and the silicon atom to which R³is bonded. In some such embodiments, the divalent hydrocarbon groupcomprises, alternatively is, an alkylene group having the generalformula —(CH₂)_(d)—, where subscript d is from 2 to 6. The divalenthydrocarbon group may include an ether moiety.

In yet other embodiments, R³ comprises an epoxy functional moiety. Inthese embodiments, R³ comprises an epoxide group. Specific examples ofsuitable epoxide groups include those of the formula:

or the formula:

As with the acryloxy functional group above, when R³ comprises theacryloxy group, R³ typically includes a divalent hydrocarbon groupbetween the epoxide group and the silicon atom to which R³ is bonded. Insome such embodiments, the divalent hydrocarbon group comprises,alternatively is, an alkylene group having the general formula—(CH₂)_(g)—, where subscript g is from 2 to 10. In other embodiments,the divalent hydrocarbon group comprises from 2 to 10 carbon atoms andincludes at least one ether moiety, i.e., at least one oxygenheteroatom.

In certain embodiments in which R³ comprises an epoxy functional moiety,specific examples of R³ include a 3-glycidoxypropyl group, a4-glycidoxybutyl group, or similar glycidoxyalkyl groups; a2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propylgroup, or similar epoxycyclohexylalkyl groups; and a 4-oxiranylbutylgroup, an 8-oxiranyloctyl group.

In certain embodiments, R³ comprises an alkoxysilyl group of theformula:

where each R is independently selected and as defined above; andsubscript c′ is 0, 1, or 2. In some such embodiments, each R is —CH₃. Inthese or other embodiments, subscript c′ is 0. In some such embodiments,the divalent hydrocarbon group comprises, alternatively is, an alkylenegroup having the general formula —(CH₂)_(g)—, where subscript g is from2 to 10. In other embodiments, the divalent hydrocarbon group comprisesfrom 2 to 10 carbon atoms and includes at least one ether moiety, i.e.,at least one oxygen heteroatom.

Method of Preparing the Branched Organosilicon Compound

A method of preparing the branched organosilicon compound (the“preparation method”) is also provided. The preparation method includesreacting an organosilicon compound and a functional compound in thepresence of a hydrosilylation catalyst to give the branchedorganosilicon compound.

As will be understood by one of skill in the art in view of thedescription herein, the organosilicon compound utilized in thepreparation method forms a portion of the branched organosiliconcompound corresponding to the organosilicon moiety represented by thesubformula R¹ ₃Si—, and the functional compound utilized in thepreparation method forms a portion of the branched organosiliconcompound corresponding to the moiety Y.

The divalent linking group X of the organosilicon compound is generallyformed during the preparation method by the reaction of theorganosilicon compound and the functional compound. This is the casewhen Y of the branched organosilicon compound has one of formulas (I) or(II). More specifically, as will be understood in view of thedescription herein, the preparation method generally includes couplingtogether the organosilicon compound and the functional compound viahydrosilylation reaction. As such, the organosilicon compound and thefunctional compound each comprise a hydrosilylatable group, which areselected to facilitate the hydrosilylative coupling of the compounds.Said differently, and as described in further detail below, one of theorganosilicon compound and the functional compound comprises anethylenically unsaturated group, and the other comprises asilicon-bonded hydrogen atom. The hydrosilylation of thesehydrosilylatable groups, collectively, forms the divalent linking groupX of the branched organosilicon. As will be understood by those of skillin the art in view of the description herein, the hydrosilylatablegroups need not form the entire divalent linking group X, but mayinstead form a portion thereof.

In other embodiments, when Y of the branched organosilicon compound isof formula (III), R³ of the branched organosilicon compound may beformed when preparing the branched organosilicon compound as a result ofthe reaction between the organosilicon compound and the functionalcompound. Depending on the organosilicon compound utilized, theorganosilicon compound can include the moiety —[R₂SiO]_(n)—SiR₂— theterminal Si includes a hydrosilylatable group that becomes a part of R³after reaction with the functional compound.

In general, the organosilicon compound includes the silicon-bondedhydrogen atom when the functional compound includes the ethylenicallyunsaturated group, and the organosilicon compound includes thesilicon-bonded ethylenically unsaturated group when the functionalcompound includes the silicon-bonded hydrogen atom. The particularselection between these two scenarios will be made by one of skill inthe art, e.g. in view of the particular branched organosilicon compoundbeing prepared, the particular organosilicon compound being utilized,and/or the particular functional compound being utilized. Specificfactors that may be utilized in this selection include the sterics,electronics, reactivity, ease of preparation, and/or commercialavailability of the various organosilicon compounds and functionalcompounds described herein.

Organosilicon Compound

The organosilicon compound has the general formula (V):

where the organosilicon moiety represented by the subformula R¹ ₃Si— isas defined above with respect to the branched organosilicon compound,and the moiety R⁷ comprises, alternatively is, a hydrosilylatable group.

More specifically, with reference to formula (V), each R¹ is generallyselected from R and —OSi(R⁴)₃, with the proviso that at least one R¹ is—OSi(R⁴)₃; each R⁴ is selected from R, —OSi(R⁵)₃, and —[OSiR₂]_(m)OSiR₃;each R⁵ is selected from R, —OSi(R⁶)₃, and —[OSiR₂]_(m)OSiR₃; and eachR⁶ is selected from R and —[OSiR₂]_(m)OSiR₃; with the proviso that atleast one of R⁴, R⁵ and R⁶ is —[OSiR₂]_(m)OSiR₃. In each instance, eachR is independently a substituted or unsubstituted hydrocarbyl group, andeach subscript m is selected such that 0≤m≤100. Notwithstanding theabove, one of skill in the art will readily understand the particularvariations of limitations of the organosilicon moiety R¹ ₃Si— in view ofthe description of the branched organosilicon compound above.

With continued reference to the organosilicon compound of formula (V),and as will be understood in view of the description herein, R⁷comprises one of the hydrosilylatable groups, which, collectively, formthe divalent linking group X of the branched organosilicon. Inparticular, R⁷ may be H or comprise a silicon-bonded hydrogen atom, orR⁷ may comprise an ethylenically unsaturated group. As introduced above,when R⁷ is H or comprises a silicon-bonded hydrogen atom, the functionalcompound includes an ethylenically unsaturated group. Likewise, when R⁷comprises the ethylenically unsaturated group, the functional compoundcomprises a silicon-bonded hydrogen atom. In specific embodiments, R⁷ isH, such that the organosilicon compound has the general formula(R¹)₃SiH, where each R¹ is independently selected and as defined above.In other embodiments, R⁷ comprises a silicon-bonded hydrogen atom or theethylenically unsaturated group.

Examples of ethylenically unsaturated groups generally includesubstituted or unsubstituted hydrocarbon groups having at least onealkene or alkyne functional group. For example, in certain embodiments,R⁷ comprises, alternatively is, an alkenyl group or an alkynyl group.Specific examples thereof include H₂C═CH—, H₂C═CHCH₂—, H₂C═CHCH₂CH₂—,H₂C═CH(CH₂)₃—, H₂C═CH(CH₂)₄—, H₂C═C(CH₃)—, H₂C═C(CH₃)CH₂—,H₂C═C(CH₃)CH₂CH₂—, H₂C═C(CH₃)CH₂CH(CH₃)—, H₂C═C(CH₃)CH(CH₃)CH₂—,H₂C═C(CH₃)C(CH₃)₂—, HC≡C—, HC≡CCH₂—, HC≡CCH(CH₃)—, HC≡CC(CH₃)₂—, andHC≡CC(CH₃)₂CH₂—.

In certain embodiments, R⁷ comprises a hydrosilylatable moiety havingthe general formula -[D²]_(h)-R⁹, where each D² is an independentlyselected divalent group; subscript h is 0 or from 1 to 10; and R⁹ is asilicon bonded hydrogen atom or an alkenyl group of formula —(R¹⁰)CCH₂,where R¹⁰ is a hydrocarbyl group having from 1 to 6 carbon atoms, analkoxy group, a silyl group, or H. In certain embodiments, R¹⁰ is H or—CH₃. In these or other embodiments, subscript h≥1 and D² is selectedfrom substituted and unsubstituted hydrocarbon groups, siloxane groups,silyl groups, and combinations thereof. In specific embodiments,subscript h is 1; D² comprises a moiety having the formula—[OSi(R)₂]_(n)OSi(R)₂—, where each R is independently selected and asdefined above and 0≤n≤10; and R⁹ is H (i.e., the silicon bonded hydrogenatom). In some embodiments, R⁷ has the general formula—X¹—[OSi(R)₂]_(n)OSi(R)₂—R⁹, where X¹ is a divalent linking group;0≤n≤10; and each R and R⁹ is independently selected and as definedabove. In some such embodiments, X¹ comprises, alternatively is, analkylene group having the general formula —(CH₂)_(d)—, where subscript dis from 2 to 6; and R⁹ is H (i.e., the silicon bonded hydrogen atom).

As will be appreciated from the description of the branchedorganosilicon compound, which will be understood to equally apply to thepreparation method unless indicated otherwise, the selection of each ofR, R¹, R⁴, R⁵, R⁶, and subscript m, where present, is not limited, andincludes any and all selections and combination of selections necessaryfor preparing the branched organosilicon compound as described above.For example, in certain embodiments, the organosilicon compound has thegeneral formula (V) where each R¹ is independently of the formula—OSi(R⁴)₃, where at least one R⁴ is —[OSiR₂]_(m)OSiR₃, and where each Rand m are independently selected and as defined above.

In these or other embodiments, the organosilicon compound has thegeneral formula:

where each R, R⁵, and R⁷ is independently selected and as defined above;and subscript j is 0, 1, or 2. In some such embodiments, subscript j is0, such that the organosilicon compound has the formula:

where each R, R⁵, and R⁷ is independently selected and as defined above.In other such embodiments, subscript j is 1, such that the organosiliconcompound has the formula:

where each R, R⁵, and R⁷ is independently selected and as defined above.In yet other such embodiments, subscript j is 2, such that theorganosilicon compound has the formula:

where each R, R⁵, and R⁷ is independently selected and as defined above.

Functional Compound

The functional compound has the general formula R⁷—Y¹, where R⁷comprises a silicon-bonded hydrogen atom or the ethylenicallyunsaturated group, and Y¹ is a functional moiety described in furtherdetail below.

As introduced above with respect to the organosilicon compound, R⁷ ofthe functional compound comprises one of the hydrosilylatable groups,which, collectively, form the divalent linking group X of the branchedorganosilicon. As such, R⁷ of the functional compound may comprise asilicon-bonded hydrogen atom or an ethylenically unsaturated group.Likewise, when R⁷ of the functional compound comprises a silicon-bondedhydrogen atom, the organosilicon compound an ethylenically unsaturatedgroup. Similarly, when R⁷ of the functional compound comprises theethylenically unsaturated group, the organosilicon compound comprises asilicon-bonded hydrogen atom.

Specific examples of suitable hydrosilylatable groups for R⁷ of thefunctional compound include those described above with respect to theorganosilicon compound. For example, in certain embodiments, R⁷ of thefunctional compound comprises, alternatively is, an alkenyl group or analkynyl group, such as any of those described above. As another example,in certain embodiments, R⁷ of the functional compound comprises ahydrosilylatable moiety having the general formula R⁹-[D²]_(h)-, whereeach D² is an independently selected divalent group; subscript h is 0 orfrom 1 to 10; and R⁹ is a silicon bonded hydrogen atom or an alkenylgroup of formula CH₂C(R¹⁰)—, where R¹⁰ is a hydrocarbyl group havingfrom 1 to 6 carbon atoms, an alkoxy group, a silyl group, or H. In someembodiments, R⁷ of the functional compound has the general formulaR⁹—Si(R)₂O[Si(R)₂O]_(n)—X¹—, where X¹ is a divalent linking group;0≤n≤10; and each R and R⁹ is independently selected and as definedabove. In some such embodiments, X¹ comprises, alternatively is, analkylene group having the general formula —(CH₂)_(d)—, where subscript dis from 2 to 6; and R⁹ is H (i.e., the silicon bonded hydrogen atom).

As introduced above, Y¹ of the functional compound is a functionalmoiety. The functional moiety generally corresponds to the moiety Y ofthe branched organosilicon compound described above. However, variationsof the functional compound generally, and in Y¹ and R⁷ of the functionalcompound in particular, may be utilized in order to prepare the branchedorganosilicon compound, as will be understood in view of the descriptionherein.

In certain embodiments, Y¹ of the functional compound is selected fromone of formulas (I) and (II):

where each R is an independently selected substituted or unsubstitutedhydrocarbyl group; each D¹ is an independently selected divalenthydrocarbon group; each subscript a is independently 0 or 1; eachsubscript b is independently 0 or 1; each subscript e is independently 1or 2; each subscript f is independently 0 or 1, with the proviso thatwhen f is 1, b is 1; subscript t is ≥0; and subscript u is >0.

In particular embodiments, Y¹ has the formula (I) and R⁷ is H (i.e., R⁷is the silicon bonded hydrogen atom). In such embodiments, thefunctional compound has the formula (VI):

where each R, D¹, subscript a, subscript b, subscript e, and subscript fis independently selected and as defined above.

In certain embodiments, Y¹ has the formula (II) and R⁷ is H (i.e., R⁷ isthe silicon bonded hydrogen atom). In such embodiments, the functionalcompound has the formula (VII):

where each R, D¹, subscript t, and subscript u is independently selectedand as defined above.

In general embodiments, Y¹ of the functional compound is not limited tothe moieties of formulas (I) and (II), but may instead be selected fromhalogen moieties, acryloxy moieties, alkoxysilyl moieties, epoxymoieties, and combinations thereof.

In certain embodiments, Y¹ has the general formula -[D³]_(i)-R³, whereD³ is a divalent group, subscript i is 0 or 1; and R³ is a halogen atom,an acryloxy group, an alkoxysilyl group, or an epoxide group. Examplesof divalent linking groups suitable for D³ (i.e., when subscript i is 1)include substituted and unsubstituted hydrocarbon groups, siloxanegroups, silyl groups, and combinations thereof. In specific embodiments,D³ comprises, alternatively is, a moiety having the formula—[OSi(R)₂]_(n)OSi(R)₂—, where each R is independently selected and asdefined above; and 0≤n≤10. In some such embodiments, D³ comprises,alternatively is, an alkylene group having the general formula—(CH₂)_(d)—, where subscript d is from 2 to 6. In some embodiments, D³comprises an ether.

In some embodiments, R³ is chlorine or bromine. In other embodiments, R³is an acryloxy group of the formula:

where R⁸ is independently selected from hydrocarbyl groups and H. Insome such embodiments, R⁸ is H or —CH₃. In certain embodiments, R³ is analkoxysilyl group of the formula:

where each R is independently selected and as defined above; andsubscript c′ is 0, 1, or 2. In some such embodiments, each R is —CH₃. Inthese or other embodiments, subscript c′ is 0. In particularembodiments, R³ is an is an epoxide group having the formula:

or the formula:

In specific embodiments, the functional compound has the generalformula: R⁷—[Si(R)₂O]_(n)—Si(R)₂—R³, where each R, R³, and R⁷ isindependently selected and as defined above; and 0≤n≤10. In some suchembodiments, R⁷ is H (i.e., the silicon bonded hydrogen atom). In otherembodiments, the functional compound has the general formulaR⁷—[CH₂]_(n′)—[O]_(m′)—[CH₂]_(o′)—R³, where R³ is independently selectedand as defined above; R⁷ is an alkenyl group or an alkynyl group;subscript n′ is 0 or from 1 to 4; subscript m′ is 0 or 1; and subscripto′ is 0 or from 1 to 4.

Hydrosilylation Catalyst

The hydrosilylation catalyst is not limited and may be any knownhydrosilylation catalyst for catalyzing hydrosilylation reactions.Combinations of different hydrosilylation catalysts may be utilized.

In certain embodiments, the hydrosilylation catalyst comprises a GroupVIII to Group XI transition metal. Group VIII to Group XI transitionmetals refer to the modern IUPAC nomenclature. Group VIII transitionmetals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs);Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium(Ir); Group X transition metals are nickel (Ni), palladium (Pd), andplatinum (Pt); and Group XI transition metals are copper (Cu), silver(Ag), and gold (Au). Combinations thereof, complexes thereof (e.g.organometallic complexes), and other forms of such metals may beutilized as the hydrosilylation catalyst.

Additional examples of catalysts suitable for the hydrosilylationcatalyst include rhenium (Re), molybdenum (Mo), Group IV transitionmetals (i.e., titanium (Ti), zirconium (Zr), and/or hafnium (Hf)),lanthanides, actinides, and Group I and II metal complexes (e.g. thosecomprising calcium (Ca), potassium (K), strontium (Sr), etc.).Combinations thereof, complexes thereof (e.g. organometallic complexes),and other forms of such metals may be utilized as the hydrosilylationcatalyst.

The hydrosilylation catalyst may be in any suitable form. For example,the hydrosilylation catalyst may be a solid, examples of which includeplatinum-based catalysts, palladium-based catalysts, and similar noblemetal-based catalysts, and also nickel-based catalysts. Specificexamples thereof include nickel, palladium, platinum, rhodium, cobalt,and similar elements, and also platinum-palladium,nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten,nickel-molybdenum, and similar catalysts comprising combinations of aplurality of metals. Additional examples of solid catalysts includeCu—Cr, Cu—Zn, Cu—Si, Cu—Fe—Al, Cu—Zn—Ti, and similar copper-containingcatalysts, and the like.

The hydrosilylation catalyst may be in or on a solid carrier. Examplesof carriers include activated carbons, silicas, silica aluminas,aluminas, zeolites and other inorganic powders/particles (e.g. sodiumsulphate), and the like. The hydrosilylation catalyst may also bedisposed in a vehicle, e.g. a solvent which solubilizes thehydrosilylation catalyst, alternatively a vehicle which merely carries,but does not solubilize, the hydrosilylation catalyst. Such vehicles areknown in the art.

In specific embodiments, the hydrosilylation catalyst comprisesplatinum. In these embodiments, the hydrosilylation catalyst isexemplified by, for example, platinum black, compounds such aschloroplatinic acid, chloroplatinic acid hexahydrate, a reaction productof chloroplatinic acid and a monohydric alcohol, platinumbis(ethylacetoacetate), platinum bis(acetylacetonate), platinumchloride, and complexes of such compounds with olefins ororganopolysiloxanes, as well as platinum compounds microencapsulated ina matrix or core-shell type compounds. Microencapsulated hydrosilylationcatalysts and methods of their preparation are known in the art, asexemplified in U.S. Pat. Nos. 4,766,176 and 5,017,654, which areincorporated by reference herein in their entireties.

Complexes of platinum with organopolysiloxanes suitable for use as thehydrosilylation catalyst include1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes with platinum.These complexes may be microencapsulated in a resin matrix.Alternatively, the hydrosilylation catalyst may comprise1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum. Thehydrosilylation catalyst may be prepared by a method comprising reactingchloroplatinic acid with an aliphatically unsaturated organosiliconcompound such as divinyltetramethyldisiloxane, or alkene-platinum-silylcomplexes. Alkene-platinum-silyl complexes may be prepared, for exampleby mixing 0.015 mole (COD)PtCl₂ with 0.045 mole COD and 0.0612 molesHMeSiCl₂, where COD represents cyclooctadiene.

Additional examples of suitable hydrosilylation catalysts for componentare described in, for example, U.S. Pat. Nos. 3,159,601; 3,220,972;3,296,291; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,784,879;5,036,117; and 5,175,325; the disclosures of which are incorporatedherein by reference in their entireties.

The hydrosilylation catalyst may also, or alternatively, be aphotoactivatable hydrosilylation catalyst, which may initiate curing viairradiation and/or heat. The photoactivatable hydrosilylation catalystcan be any hydrosilylation catalyst capable of catalyzing thehydrosilylation reaction, particularly upon exposure to radiation havinga wavelength of from 150 to 800 nanometers (nm).

Method

The organosilicon compound and the functional compound are typicallyreacted in a molar ratio of from 1.5:1 to 1:1.5, alternatively from1.4:1 to 1:1.4, alternatively from 1.3:1 to 1:1.3, alternatively from1.2:1 to 1:1.2, alternatively from 1.1:1 to 1:1.1, alternatively from1.1:1 to 1:1. However, one of skill in the art will select theparticular ratios utilized, e.g. in view of the particular branchedorganosilicon compound being prepared, the particular organosiliconcompound and/or functional compound being utilized, a desired use of thebranched organosilicon compound, etc.

Other methods of preparing the branched organosilicon compound can bereadily envisaged by one of skill in the art based on modifications orreplacements of functional groups and reaction schemes. For example, insome embodiments, the branched organosilicon compound may be preparedfrom an organosilicon compound and a functional compound that bothcomprise the same type of hydrosilylatable group, e.g. both comprise anethylenically unsaturated group or both comprise a silicon-bondedhydrogen atom. In such embodiments, a converter compound may be utilizedin a first hydrosilylation reaction, i.e., to convert thehydrosilylatable group of one of the organosilicon compound and thefunctional compound into the other type of hydrosilylatable group, e.g.by hydrosilylating the converter compound thereto. Examples of suitableconverter compounds include those comprising at least two silicon-bondedhydrogen atoms or at least two ethylenically unsaturated groups, as wellas compounds comprising at least one silicon-bonded hydrogen atom and afunctional group readily transformed into the same, and compoundscomprising at least one ethylenically unsaturated group and a functionalgroup readily transformed into the same.

The Copolymer

A copolymer is also provided. The copolymer comprises the reactionproduct of the branched organosilicon compound and a second compoundreactive with the branched organosilicon compound (hereinafter, the“reactive compound”). As will be appreciated by one of skill in the artin view of the description herein, many various of the copolymer may beprepared, e.g. depending on the particular branched organosiliconcompound utilized, the particular reactive compound utilized, the typeof reaction performed, the ratio of components utilized, etc. Forexample, the second compound is generally selected based on R³ of thebranched organosilicon compound. When R³ comprises an acryloxyfunctional moiety, the reactive compound is typically acrylatefunctional. When R³ comprises an epoxy functional moiety, the reactivecompound typically comprises an epoxy-reactive compound, e.g. anamino-functional compound. When R³ comprises an alkoxysilyl functionalmoiety, the alkoxysilyl functional moiety may be cohydrolyzed orcocondensed with other hydrolysable groups.

In general, the copolymer comprises a branched organosilicon moietyhaving the formula:

which is formed from the branched organosilicon compound utilized in thereaction with the reactive compound. As such, with regard to thebranched organosilicon moiety of the copolymer, the organosilicon moietyrepresented by the subformula R¹ ₃Si— is as defined above with respectto the branched organosilicon compound and the method of forming thesame. Likewise, subformula —X— represents the divalent linking groupdefined above with respect to the branched organosilicon compound andthe method of forming the same. Subformula —Y²— is a moiety formed fromthe moiety Y of the branched organosilicon compound (i.e., during thereaction of the branched organosilicon compound the reactive compound),as described in further detail below.

Polymer Moiety (of Copolymer)

The copolymer also comprises a polymer moiety. The polymer moiety is notparticularly limited, and may comprise, alternatively may be, anypolymer or combination of polymers that may be grafted onto or reactedwith the branched organosilicon compound. In addition, the polymermoiety may be formed in situ in the presence of the branchedorganosilicon compound, i.e., the polymer moiety need not be formedprior to forming the copolymer. Examples of such polymers includepolyethers, polyacrylates, polyesters, polycarbonates, and the like, aswell as combinations thereof. However, as will be understood in view ofthe description herein, the polymer moiety may be any moiety comprisingat least one polymer group.

Specific examples of the at least one polymer group include polyethergroups, polyacrylate groups, polyester groups, polycarbonate groups,alkylaluminoxane groups, alkylgermoxane groups, polythioester groups,polythioether groups, polyacrylonitrile groups, polyacrylamide groups,epoxy groups, polyurethane groups, polyurea groups, polyacetal groups,polyolefin groups, polyvinyl alcohol groups, polyvinyl ester groups,polyvinyl ether groups, polyvinyl ketone groups, polyisobutylene groups,polychloroprene groups, polyisoprene groups, polybutadiene groups,polyvinylidiene groups, polyfluorocarbon groups, polychlorinatedhydrocarbon groups, polyalkyne groups, polyamide groups, polyimidegroups, polyimidazole groups, polyoxazole groups, polyoxazine groups,polyoxidiazole groups, polythiazole groups, polysulfone groups,polysulfide groups, polyketone groups, polyetherketone groups,polyanhydride groups, polyamine groups, polyimine groups,polyphosphazene groups, polysaccharide groups, polypeptide groups,polyisocyante groups, cellulosic groups, and combinations thereof.

In certain embodiments, the polymer moiety comprises a combination ofpolymers, i.e., is a copolymer moiety comprising at least two differentpolymer groups. In such embodiments, each of the polymer groups may beindependently selected, and may include any of the polymers or polymergroups described herein.

Polyacrylates

In some embodiments, the polymer moiety comprises, alternatively is, apolyacrylate moiety. The polyacrylate moiety is not limited and may beformed from any acrylate compound, as described in further detail below.The term “polyacrylate moiety,” as used herein, means a moiety includingat least two acrylate functional groups (e.g. alkyl acrylate groups suchas methyl, ethyl, or butyl acrylate groups, substituted acrylate groupssuch as a 2-ethylhexyl or hydroxyl ethyl groups, and others such as amethylolpropane acrylate groups, etc.). As will be understood in view ofthe description herein, the polyacrylate moiety may be monomeric,oligomeric, polymeric, aliphatic, aromatic, araliphatic, etc. Inaddition, the copolymer may comprise a number of different polyacrylatemoieties, which are independently selected.

Methods of preparing polyacrylates (and polyacrylate moieties) are knownin the art. For example, polyacrylates may be prepared via aconventional radical polymerization of acrylic monomers. Suchconventional methods are generally carried out by combiningradically-polymerizable monomers (e.g. acrylate monomers, comonomers,etc.) in the presence of a radical initiator/generator, such as athermo-, chemo, and/or photopolymerization initiator. For example,peroxides and aromatic initiators (e.g. phenols, benzoins, heterocylclessuch as imidazoles, etc.) are commonly utilized. These conventionalmethods may be used to prepare acrylate homopolymers and copolymers,including ternary, quaternary, and higher-order copolymers.Additionally, di- and/or multifunctional acrylic monomers may also beutilized, e.g. to prepare multifunctional polyacrylates (andpolyacrylate moieties), as will be understood in view of the descriptionof suitable acrylic monomers herein.

In general, methods of preparing polyacrylates (and polyacrylatemoieties) utilize at least one acrylic monomer having an acryloyloxy oralkylacryloyloxy group (i.e., acrylates, alkylacrylates, acrylic acids,alkylacrylic acids, and the like, as well as derivatives and/orcombinations thereof). Such acrylic monomers may be monofunctional orpolyfunctional acrylic monomers.

Examples of specific monofunctional acrylic monomers suitable forpreparing polyacrylates (and polyacrylate moieties) include(alkyl)acrylic compounds, such as methyl acrylate, phenoxyethyl(meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate,2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl(meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate,polyoxyethylene-modified p-cumylphenol (meth)acrylate,2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl(meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate,polyoxyethylene-modified phenoxy (meth)acrylate,polyoxypropylene-modified phenoxy (meth)acrylate, polyoxyethylenenonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl(meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl(meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate,dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate,cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate,acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate,ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate,butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate,t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate,hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate,isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl(meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl(meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl(meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate,1-naphthylmethyl (meth)acrylate, 2-naphthylmethyl (meth)acrylate,tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate,ethoxydiethylene glycol (meth)acrylate, poly(ethylene glycol)mono(meth)acrylate, poly(propylene glycol) mono(meth)acrylate,methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate,methoxypoly(ethylene glycol) (meth)acrylate, methoxypoly(propyleneglycol) (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl(meth)acrylamide, N,N-dimethyl (meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and thelike, as well as derivatives thereof.

Examples of specific polyfunctional acrylic monomers suitable forpreparing polyacrylates (and polyacrylate moieties) include(alkyl)acrylic compounds having two or more acryloyl or methacryloylgroups, such as trimethylolpropane di(meth)acrylate, trimethylolpropanetri(meth)acrylate, polyoxyethylene-modified trimethylolpropanetri(meth)acrylate, polyoxypropylene-modified trimethylolpropanetri(meth)acrylate, polyoxyethylene/polyoxypropylene-modifiedtrimethylolpropane tri(meth)acrylate, dimethyloltricyclodecanedi(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethyleneglycol di(meth)acrylate, phenylethylene glycol di(meth)acrylate,poly(ethylene glycol) di(meth)acrylate, poly(propylene glycol)di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanediol di(meth)acrylate,1,3-adamantanedimethanol di(meth)acrylate, o-xylylene di(meth)acrylate,m-xylylene di(meth)acrylate, p-xylylene di(meth)acrylate,tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate,dipentaerythritol penta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, polyoxyethylene-modified2,2-bis(4-((meth)acryloxy)phenyl)propane, polyoxypropylene-modified2,2-bis(4-((meth)acryloxy)phenyl)propane, andpolyoxyethylene/polyoxypropylene-modified2,2-bis(4-((meth)acryloxy)phenyl)propane.

It is to be appreciated that the (alkyl)acrylic compounds above aredescribed in terms of (meth)acrylate species only for brevity, and thatone of skill in the art will readily understand that other alkyl and/orhydrido versions of such compounds may equally be utilized. For example,one of skill in the art will understand that the monomer “2-ethylhexyl(meth)acrylate” listed above exemplifies both 2-ethylhexyl(meth)acrylate as well as 2-ethylhexyl acrylate. Likewise, while theacrylic monomers are described generally as propenoates (i.e.,α,β-unsaturated esters) in the examples above, it is to be appreciatedthat the that the term “acrylate” used in these descriptions may equallyrefer to an acid, salt, and/or conjugate base of the esters exemplified.For example, one of skill in the art will understand that the monomer“methyl acrylate” listed above exemplifies the methyl ester of acrylicacid, as well as acrylic acid, acrylate salts (e.g. sodium acrylate),etc. Furthermore, multifunctional derivatives/variations of the acrylicmonomers described above may also be utilized. For example, the monomers“ethyl (meth)acrylate” listed above exemplifiesfunctionalized-derivatives, such as substituted ethyl (meth)acrylatesand ethyl acrylates (e.g. hydroxyethyl (meth) acrylate and hydroxyethylacrylate, respectively).

Comonomers (i.e., monomers reactive with the acrylic monomers above) mayalso be utilized to prepare the polyacrylates (and polyacrylatemoieties). Such monomers are not limited, and generally includecompounds having a radically polymerizable group, such as an alkenyl,acryloyl, and alkylacryloyl groups. In general, comonomers are selectedby one of skill the in art, e.g. to alter a property of the polyacrylatemoiety and/or the copolymer comprising the polyacrylate moiety, to beprepared. For example, it is known in the art that styrene may becopolymerized with an acrylic monomer to prepare polyacrylates (andpolyacrylate moieties) having increased hardness as compared to thoseabsent such styrene comonomers. Likewise, comonomers such asacrylonitrile may be utilized to increase interchain polar interactions,and thus increase tensile strength and ultimate elongation ofpolyacrylates (and polyacrylate moieties), while also decreasing lowtemperature flexibility of such polyacrylates (and polyacrylatemoieties). Moreover, one of skill in the art will readily selected theproportion(s) of monomers utilized, the order of addition, the length ofreaction, and other factors to independently tune various properties(e.g. flexibility, solubility, hardness, polarity, etc.) of thepolyacrylate moiety, the copolymer comprising the polyacrylate moiety,and/or compositions and/or products prepared therefrom. Specificexamples of suitable comonomers include styrene, acrylonitrile,vinylidene chloride, vinyl chloride, ethylene, propylene, butylene,chloroprene, isoprene, tetrafluoroethylene, and the like, as well asderivatives thereof.

It is to be appreciated that combinations of acrylic monomers may alsobe utilized to prepare the polyacrylates, such that the polyacrylates(and polyacrylate moieties) may be homopolymeric or copolymeric withrespect to any repeating segments therein. For example, the methodsdescribed above may be utilized to prepare multifunctionalpolyacrylates, e.g. by utilizing a monofunctional acrylic monomer and apolyfunctional acrylic monomer. These different functional monomers aretypically selected by one of skill in the art, e.g. based on thereactivity and interpolymeric and/or intrapolymeric interactivity, toalter the mechanical strength of the polyacrylate prepared therewith.For example, cured products comprising the copolymer utilizing apolyacrylate moiety comprising a combination of monofunctional acrylicmonomers and polyfunctional acrylic monomers can be prepared withincreased mechanical strength as compared to those utilizing ahomopolymeric polyacrylate moieties. Likewise, cured products comprisingthe copolymer utilizing a homopolymeric polyacrylate moiety may beprepared having increased flexibility as compared to those utilizing apolyfunctional polyacrylate moieties.

In specific embodiments, the polyacrylate moiety of the copolymer isprepared from methyl (meth)acrylate, methyl acrylate, butyl(meth)acrylate, butyl acrylate, 2-ethylhexyl (meth)acrylate,2-ethylhexyl acrylate, hydroxyethyl (meth)acrylate, hydroxyethylacrylate, methylacrylic acid, acrylic acid, and/or styrene monomers.

It will also be appreciated that polyacrylates (and polyacrylatemoieties) prepared as described above may be mono- or multifunctionalwith respect to the non-acrylic functional groups present therein. Forexample, such methods may be utilized to prepare polyacrylate alcohols,diols and/or polyols, including via the methods described above (e.g. byutilizing a hydroxyl-functional monomer) and modifications thereof (e.g.by utilizing a post-polymerization functionalization technique, such asendcapping and/or grafting a functional group-containing compound onto apolyacrylate. Such functional group-containing compounds includealkoxysilyl groups, e.g. which may be grafted onto a polyacrylate viahydrosilylation or other methods known in the art. For example, incertain embodiments, the polyacrylate moiety is prepared from apolyacrylate polyol. In these or other embodiments, the polyacrylatemoiety is prepared from a polyacrylate compound comprising adimethoxymethylsily group. In certain embodiments, the polyacrylatemoiety is prepared from a polyacrylate compound comprising at least oneradical polymerizable group, such as an acryloyl functional group.

The particular polyacrylate moiety present in the copolymer is afunction of end use applications of the copolymer. For example,aliphatic polyacrylate moieties generally provide greater flexibilityand lesser glass transition temperatures (T_(g)) than aromaticpolyacrylate moieties, which are typically more rigid with greater glasstransition temperatures (T_(g)). Similarly, molecular weight andviscosity may be selected controlled based on desired properties of thecopolymer. Further still, the selection of any polyacrylate moiety canbe a function of which functional moiety Y is present in the branchedorganosilicon compound being reacted to form the copolymer, whether thepolymer moiety of the copolymer will include any other polymers otherthan the polyacrylate moiety, etc.

When present, each polyacrylate moiety typically has a number averagemolecular weight (M_(n)) of at least about 100. In certain embodiments,at least one polyacrylate has a M_(n) of at least 100, alternatively atleast 125, alternatively at least 150, alternatively at least 200,alternatively at least 250, alternatively at least 300. In these orother embodiments, each polyacrylate moiety has a M_(n) of at least 200,alternatively at least 300, alternatively at least 400, alternatively atleast 500, alternatively at least 600, alternatively at least 700,alternatively at least 1,000, alternatively at least 2,000,alternatively at least 4,000, alternatively at least 8,000. In certainembodiments, each polyacrylate moiety has a maximum M_(n) of 20,000,alternatively less than 19,000, alternatively less than 18,000,alternatively less than 17,000, alternatively less than 16,000,alternatively less than 15,000. The number average molecular weight maybe readily determined using Gel Permeation Chromatography (GPC)techniques based on polystyrene standards.

Polyethers

In some embodiments, the polymer moiety comprises, alternatively is, apolyether moiety. The term “polyether moiety,” as used herein, means amoiety including at least two ether functional groups. As will beunderstood in view of the description herein, the polyether moiety maybe monomeric, oligomeric, polymeric, aliphatic, aromatic, araliphatic,etc. In addition, the may comprise a number of different polyethermoieties, which are independently selected.

Each polyether moiety typically comprises a polyether having the generalformula —O—(C_(n) ¹H_(2n′)O)_(w′)—, wherein subscript n′ isindependently selected from 2 to 4 in each moiety indicated by subscriptw′; and wherein subscript w′ is from 1 to 1000. In certain embodiments,the polyether moiety comprises multiple polyethers of such a generalformula, which may be present in a linear or branched form with otherpolyethers to form a polyether moiety comprising multipleoxyalkylene-based polyethers. In such embodiments, the polyether moietymay comprise oxyethylene units (C₂H₄O), oxypropylene units (C₃H₆O),oxybutylene or oxytetramethylene units (C₄H₈O), or mixtures thereof,which may be in block form or randomized in the polyether moiety. Theoxyalkylene units in the polyether moiety may independently be linear orbranched. For example, oxyethylene units, if present, may be of formula—CH₂CH₂O— or of formula —CHCH₃O—. Similarly, oxypropylene units may beof formula —CH₂CH₂CH₂O—, —CH₂CHCH₃O—, or —CHCH₃CH₂O—.

For example, the polyether moiety may comprise a polyether having thegeneral formula —O—(C₂H₄O)_(x′)(C₃H₆O)_(y′)(C₄H₈O)_(z′)—, whereinsubscript x′ is from 0 to 999; subscript y′ is from 1 to 1000; andsubscript z′ is from 0 to 999; and wherein units indicated by subscriptsx′, y′ and z′ may be in randomized or block form in the polyethermoiety. In certain embodiments, x′ and z′ are each 0 such that thepolyether of the polyether moiety has the general formula—O—(C₃H₆O)_(y′)—, where y′ is defined above.

In some embodiments, the polyether moiety comprises a polyether havingthe formula -D⁴-O—(C_(n′)H_(2n′)O)_(w′-D) ⁴-. In such embodiments, eachD⁴ is an independently selected divalent hydrocarbon group having from 1to 6 carbon atoms, alternatively from 1 to 5 carbon atoms, alternativelyfrom 1 to 4 carbon atoms, alternatively 1 or 2 carbon atoms. Each D⁴ mayindependently be linear or branched. For example, when D⁴ has two carbonatoms, D⁴ has formula C₂H₄, and may be linear (CH₂CH₂) or branched(CHCH₃). In certain embodiments, D⁴ is linear. Any D⁴ may be the same asor different from any particular D⁴. In specific embodiments, each D⁴ isCH₂. Each subscript n′ is independently selected from 2 to 4 in eachmoiety indicated by subscript w′, and subscript w′ is defined above.

For example, in such embodiments, the polyether moiety may comprise apolyether having the formula-D⁴-O—(C₂H₄O)_(x′)(C₃H₆O)_(y′)(C₄H₈O)_(z′)-D⁴-, wherein subscript x′ isfrom 0 to 999; subscript y′ is from 1 to 1000; and subscript z′ is from0 to 999; and wherein units indicated by subscripts x′, y′ and z′ may bein randomized or block form in the polyether. In certain embodiments, x′and z′ are each 0 such that the polyether has the formula-D⁴-O—(C₃H₆O)_(y′)-D⁴-, where D⁴ and y′ are defined above. In specificembodiments, each D⁴ is also C₃H₆. When x′ and z′ are each 0 and each D⁴is C₃H₆, the polyether of the polyether moiety has the formula—C₃H₆—O—(C₃H₆O)_(y′)—C₃H₆—, where y′ is defined above.

In certain embodiments, the polyether moiety comprises a polyetherhaving the general formula:

—CH₂—CH(R¹²)-[D⁴]_(m′)-O—[C₂H₄O]_(x′)[C₃H₆O]_(y′)[C₄H₈O]_(z′)-[D⁴]_(m′)-CH(R¹²)—CH₂—,

wherein each R¹² is independently a hydrocarbyl group having from 1 to 6carbon atoms, an alkoxy group, a silyl group, or H; each D⁴ is anindependently selected divalent group having from 1 to 6 carbon atoms,subscript m′ is 0 or 1, subscript x′ is from 0 to 999, subscript y′ isfrom 1 to 1000, and subscript z′ is from 0 to 999, and wherein unitsindicated by subscripts x′, y′ and z′ may be in randomized or block formin the polyether.

Each R¹² is independently selected, and may be any of the C₁-C₆hydrocarbyl groups described herein. For example, R¹² may be methyl,propyl, etc. In certain embodiments, each R¹² is methyl. Alternatively,or in addition, R¹² may be H, an alkoxy group, or a silyl group.

Each subscript m′ is independently 0 or 1, such that the polyether ofthe polyether moiety may comprise 0, 1, or 2 of the divalent hydrocarbongroups D⁴. Typically, each subscript m′ is 1. However, in certainembodiments at least one subscript m is 0.

In some embodiments, the polyether moiety may be branched. In suchembodiments, the polyether may have the general formula [D⁴]_(m″)[P],where D⁴ is defined above, subscript m″ is ≥3 (e.g. 3, 4, 5, 6, 7, 8, 9,10, etc.), and P is a polyether comprising at least one of thepolyethers described above. For example, in some such embodiments, P isa polyether formed from a polyol (e.g. butane diol, glycerol, sorbitol,etc.) and a polyoxyalkylene (e.g. a polyoxypropylene), which is endcapedwith m″ number of D⁴ moieties. In such instances, the number of alcoholfunctional groups composing the polyol will correspond to the maximumnumber of m″. However, if not all polyoxyalkylene chains extending fromthe polyol are endcapped, then m″ will be less than the number ofalcohol functional groups composing the polyol.

When present, each polyether moiety, alternatively each polyether of thepolyether moiety, typically has a number average molecular weight(M_(n)) of at least about 100. In certain embodiments, at least onepolyether moiety, alternatively one polyether of the polyether moiety,has a M_(n) of at least 200, alternatively at least 300, alternativelyat least 400, alternatively at least 500, alternatively at least 600,alternatively at least 700. In these or other embodiments, eachpolyether moiety, alternatively each polyether of the polyether moiety,has a M_(n) of at least 200, alternatively at least 300, alternativelyat least 400, alternatively at least 500, alternatively at least 600,alternatively at least 700, alternatively at least 1,000, alternativelyat least 2,000, alternatively at least 4,000, alternatively at least8,000, alternatively at least 12,000, alternatively at least 16,000,alternatively at least 25,000, alternatively at least 50,000. Inspecific embodiments, at least one, alternatively each, polyethermoiety, alternatively polyether of the polyether moiety, has a M_(n) offrom 700 to 900. The number average molecular weight may be readilydetermined using Gel Permeation Chromatography (GPC) techniques based onpolystyrene standards or using end group analysis by nuclear magneticresonance spectroscopy.

Polyesters

In some embodiments, the polymer moiety comprises, alternatively is, apolyester moiety. The term “polyester moiety,” as used herein, means amoiety including at least one two ester bonds in the polymer. Forexample, the polyester moiety itself may be monomeric, oligomeric,polymeric, aliphatic, aromatic, araliphatic, etc. In addition, thecopolymer may comprise a number of different polyester moieties, whichare independently selected.

Methods of preparing polyesters (and polyester moieties) are known inthe art. For example, polyesters may be prepared via a conventionalesterification process using a hydroxyl compound (e.g. an aromaticand/or aliphatic alcohol or glycol) and an acid. The hydroxyl compoundis typically a polyhydric alcohol.

Specific examples of hydroxyl compounds suitable for preparingpolyesters (and polyester moieties) include ethylene glycol, diethyleneglycol, propylene glycol, dipropylene glycol, trimethylene glycol,1,3-propanediol, 1,2-butane diol, 1,3-butanediol, 1,4-butanediol,1,2-pentanediol, 1,4-pentanediol, neopentyl glycol, 1,5-pentanediol,1,6-hexanediol, 1,7-heptanediol, glycerol, 1,1,1-trimethylolpropane,1,1,1-trimethylolethane, 1,2,6-hexanetriol, decanediol, dodecanediolα-methyl glucoside, pentaerythritol, and sorbitol. Also included withinthe term “polyhydric alcohols” are compounds derived from phenol such as2,2-bis(4-hydroxylphenyl)propane, commonly known as Bisphenol A

Specific examples of acids suitable for preparing polyesters (andpolyester moieties) include polycarboxylic acids, including oxalic acid,malonic acid, succinic acid, glutaric acid, adipic acid,2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid, azelaic acid,sebacic acid, brassylic acid, maleic acid, fumaric acid, glutaconicacid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethyl-glutaricacid, α, β-diethylsuccinic acid, isophthalic acid, terephthalic acid,hemimellitic acid, phthalic acid, isohthalic acid and1,4-cyclohexanedicarboxylic acid.

Other methods of preparing polyesters (and polyester moieties) are alsoknown. For example, polyesters (and polyester moieties) may comprisering-opened polymers of a cyclic lactone, polycondensation products of ahydroxycarboxylic acid, and polycondensation products of a dibasic acidand a polyol.

Each particular polyester moiety present in the copolymer is a functionof end use applications of the copolymer. For example, aliphaticpolyester moieties generally provide greater flexibility and lesserglass transition temperatures (T_(g)) than aromatic polyester moieties,which are typically more rigid with greater glass transitiontemperatures (T_(g)). Similarly, molecular weight and viscosity may beselected controlled based on desired properties of the copolymer.Further still, the selection of any polyester moiety can be a functionof which functional moiety Y is present in the branched organosiliconcompound being reacted to form the copolymer, whether the polymer moietyof the copolymer will include any other polymers other than thepolyester moiety, etc.

When present, each polyester moiety typically has a number averagemolecular weight (M_(n)) of at least about 100. In certain embodiments,at least one polyester moiety has a M_(n) of at least 100, alternativelyat least 125, alternatively at least 150, alternatively at least 200,alternatively at least 250, alternatively at least 300. In these orother embodiments, each polyester moiety has a M_(n) of at least 200,alternatively at least 300, alternatively at least 400, alternatively atleast 500, alternatively at least 600, alternatively at least 700,alternatively at least 1,000, alternatively at least 2,000,alternatively at least 4,000, alternatively at least 8,000. In certainembodiments, each polyester moiety has a maximum M_(n) of 20,000,alternatively less than 19,000, alternatively less than 18,000,alternatively less than 17,000, alternatively less than 16,000,alternatively less than 15,000. The number average molecular weight maybe readily determined using Gel Permeation Chromatography (GPC)techniques based on polystyrene standards.

Polycarbonates

In some embodiments, the polymer moiety comprises, alternatively is, apolycarbonate moiety. The term “polycarbonate moiety,” as used herein,means a moiety including at least one two carbonate bonds in thepolymer. For example, the polycarbonate moiety itself may be monomeric,oligomeric, polymeric, aliphatic, aromatic, araliphatic, etc. Inaddition, the copolymer may comprise a number of different polycarbonatemoieties, which are independently selected. Examples of suitablepolycarbonate moieties are not limited, and include polycarbonates (andpolycarbonate moieties) formed from any polycarbonate compound, asdescribed in further detail below.

Methods of preparing polycarbonates (and polycarbonate moieties) areknown in the art. For example, polycarbonates may be prepared viaconventional processes, such as those utilizing a hydroxyl compound(e.g. an aromatic and/or aliphatic alcohol or glycol) in an alkoxylationof phosgene (i.e., COCl₂), a transalkoxylation of a carbonate monomer,an alkoxylation and/or transalkoxylation of an alkyl chloroformate (e.g.methyl chloroformate), or combinations thereof. The hydroxyl compound istypically a polyhydric alcohol.

Specific examples of hydroxyl compounds suitable for preparingpolycarbonates (and polycarbonate moieties) include ethylene glycol,diethylene glycol, propylene glycol, dipropylene glycol, trimethyleneglycol, 1,3-propanediol, 1,2-butane diol, 1,3-butanediol,1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, neopentyl glycol,1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol,1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, 1,2,6-hexanetriol,decanediol, dodecanediol α-methyl glucoside, pentaerythritol, andsorbitol. Also included within the term “polyhydric alcohols” arecompounds derived from phenol such as 2,2-bis(4-hydroxylphenyl)propane,commonly known as Bisphenol A.

Examples of carbonate monomers suitable for preparing polycarbonates(and polycarbonate moieties) include acyclic carbonate esters, such asdialkyl carbonates (e.g. dimethyl carbonate), diaryl carbonates (e.g.diphenyl carbonate), and cyclic carbonate esters such as ethylenecarbonate, trimethylene carbonate, etc. Other carbonate monomers mayalso be utilized, such as those prepared via conventional processes,including those utilizing a hydroxyl compound (e.g. such as thosedescribed herein) in a bisalkoxylation of phosgene or in an oxidativecarbonylation (e.g. reaction with carbon monoxide and an oxidizer). Insuch processes, the hydroxyl compound may be a monohydric alcohol, suchas an alkyl alcohol (e.g. methanol, ethanol, propanol, etc.), a phenol,etc.

Other methods of preparing polycarbonates (and polycarbonate moieties)are also known. For example, polycarbonates (and polycarbonate moieties)may comprise ring-opened polymers of an oxirane (e.g. an epoxidecompound, such as propylene oxide) and CO₂.

It will be appreciated that polycarbonates (and polycarbonate moieties)prepared as described above may be mono- or polyfunctional with respectto the functional groups present therein (e.g. in the terminalposition(s)), which are typically selected by one of skill in the art,e.g. via the particular method of preparation utilized, the order ofaddition and/or relative amounts of the compounds used to form thepolycarbonates (and polycarbonate moieties), etc. For example, suchmethods may be utilized to prepare polycarbonate diols and/orpolycarbonate polyols, e.g. via utilizing the methods of oxidativeoxirane carbonylation and/or the alkoxylation and/or transalkoxylationof the carbonate monomer and/or carbonyl chloride monomer with one ormore of the polyhydric alcohols described above. It is also to beappreciated that combinations of the hydroxyl compounds may also beutilized in any one particular method of preparation, such that thepolycarbonates (and polycarbonate moieties) may be homopolymeric orcopolymeric with respect to any repeating segments therein.

Each particular polycarbonate moiety present in the copolymer is afunction of end use applications of the copolymer. For example,aliphatic polycarbonate moieties generally provide greater flexibilityand lesser glass transition temperatures (T_(g)) than aromaticpolycarbonate moieties, which are typically more rigid with greaterglass transition temperatures (T_(g)). Similarly, molecular weight andviscosity of any particular polycarbonate moiety may be selectedcontrolled based on desired properties of the copolymer. Further still,the selection of any polycarbonate moiety can be a function of whichfunctional moiety Y is present in the branched organosilicon compoundbeing reacted to form the copolymer, whether the polymer moiety of thecopolymer will include any other polymers other than the polycarbonatemoiety, etc.

When present, each polycarbonate moiety typically has a number averagemolecular weight (M_(n)) of at least about 100. In certain embodiments,at least one polycarbonate moiety has a M_(n) of at least 100,alternatively at least 125, alternatively at least 150, alternatively atleast 200, alternatively at least 250, alternatively at least 300. Inthese or other embodiments, each polycarbonate moiety has a M_(n) of atleast 200, alternatively at least 300, alternatively at least 400,alternatively at least 500, alternatively at least 600, alternatively atleast 700, alternatively at least 1,000, alternatively at least 2,000,alternatively at least 4,000, alternatively at least 8,000. In certainembodiments, each polycarbonate moiety has a maximum M_(n) of 20,000,alternatively less than 19,000, alternatively less than 18,000,alternatively less than 17,000, alternatively less than 16,000,alternatively less than 15,000. The number average molecular weight maybe readily determined using Gel Permeation Chromatography (GPC)techniques based on polystyrene standards.

Structure of Copolymer

In some embodiments, the copolymer has the general formula:

where the organosilicon moiety represented by the subformula R¹ ₃Si— isas defined above with respect to the branched organosilicon compound;—X— represents the divalent linking group defined above with respect tothe branched organosilicon compound and the method of forming the same;—Y²— is a moiety formed from the moiety Y of the branched organosiliconcompound (i.e., during the reaction of the branched organosiliconcompound the reactive compound); and Z is the polymer moiety.

Moiety Y² is formed from the moiety Y of the branched organosiliconcompound. As such, the particular nature (e.g. structure, formula, etc.)of Y² will be controlled by the selection of the particular branchedorganosilicon compound and reactive compound to be utilized in preparingthe copolymer, the type of reaction used therewith, etc., as will beunderstood by those of skill in the art in view of the descriptionherein.

In certain embodiments, the copolymer has the general formula:

where moieties R¹ ₃Si—, —X—, —Y²—, and Z are as defined above, andsubscript x″ is ≥2. In such embodiments, the copolymer may comprise alinear structure, e.g. where subscript x″ is 2, and the polymer moiety Zis linear, such that the copolymer has the general structureR¹³Si—X—Y²—Z—Y²—X—Si—R¹ ₃. Alternatively, the copolymer may comprise abranched structure, such as where X is at least trivalent and subscriptx″ is ≥2, alternatively ≥3.

Method of Preparing the Copolymer

As introduced above, the copolymer comprises the reaction product of thebranched organosilicon compound and the reactive compound. Accordingly,a method of preparing the copolymer is further provided (the“polymerization method”). The polymerization method includes reactingthe branched organosilicon compound and the reactive compound to givethe copolymer.

Second Compound Reactive with the Branched Organosilicon Compound

The reactive compound is reactive with the branched organosiliconcompound. As the branched organosilicon compound may vary in terms ofreactivity, the reactive compound may likewise vary, and will beselected based on the particular branched organosilicon compound beingutilized in the polymerization method, the copolymer to be formed, thedesired end use of the copolymer, etc.

In general, the reactive compound has the formula (R¹¹)_(a″)—Z, where Zis the polymer moiety described above with respect to the copolymer, R¹¹comprises a functional group reactive with the branched organosiliconcompound, and subscript a″ is ≥1. Alternatively, Z may be a monomer,e.g. the copolymer may be formed by polymerizing monomers in thepresence of the branched organosilicon compound such that the polymermoiety is formed in situ. The polymer moiety Z is not limited, and maycomprise, alternatively may be, any of the polymer moieties describedabove. Moreover, the polymer moiety Z may comprise groups other than thepolymer groups and the reactive groups R¹¹, such as linking groups (e.g.divalent organic and/or silicon linking groups, such as hydrocarbonlinking groups, silyl and/or organosilyl linking groups, siloxane and/ororganosiloxane linking groups, and the like, or combinations thereof).Such linking groups may be present in the reactive compound between thepolymers of moiety Z, between the polymers of moiety Z and the reactivegroup R¹¹, or both. Subscript a″ represents the number of groups R¹¹ ofthe reactive compound that may react with the branched organosiliconcompound. For example, when subscript a″ is 1, the reactive compound maybe monoreactive, whereas when subscript a″ is 2, 3, or greater, thereactive compound may be able to react with 2, 3, or more equivalents ofthe branched organosilicon compound (e.g. to form the copolymer havingone of the branched structures described above).

Each R¹¹ is independently selected, and may comprise, alternatively maybe, any functional group reactive with the branched organosiliconcompound. For example, R¹¹ may comprise, alternatively may be, a groupreactive via a substitution reaction, an addition reaction, a radicalreaction, a coupling reaction, or combinations thereof. Specificexamples of such reactions include nucleophilic substitutions,ring-opening additions, transalkoxylations, hydrosilylations, olefinmeathesis, condensations, radical couplings and/or polymerizations, andthe like, as well as combinations thereof. Accordingly, each R¹¹ maycomprise, alternatively may be, a nucleophilic group (e.g. a hydroxylgroup, an amine group, a thiol group, a silanol group, etc.), anethylenically unsaturated group (e.g. an alkenyl or alkynyl group, suchas any of those described above), a silicon-bonded hydrogen atom, acondensable group (e.g. a carboxylic acid group, a silanol group, anamide group, etc.), or combinations thereof.

The branched organosilicon compound and the reactive compound aretypically reacted in a molar ratio of from 1.5:1 to 1:1.5, alternativelyfrom 1.4:1 to 1:1.4, alternatively from 1.3:1 to 1:1.3, alternativelyfrom 1.2:1 to 1:1.2, alternatively from 1.1:1 to 1:1.1, alternativelyfrom 1.1:1 to 1:1. However, one of skill in the art will select theparticular ratios utilized, e.g. in view of the particular copolymerbeing prepared, the particular branched organosilicon compound and/orreactive compound being utilized, a desired use of the copolymer beingprepared, the type of reaction being utilized in the polymerizationmethod, etc.

Composition & Use of Branched Organosilicon Compound and Copolymer

A composition is also provided. The composition includes at least one ofthe branched organosilicon compound (the “compound”) and the copolymer.In various embodiments, the composition comprises the compound but notthe copolymer. In certain embodiments, the composition further comprisesthe copolymer in addition to the compound. In other embodiments, thecomposition comprises the copolymer but not the compound. Thecomposition is generally without limitation, and can be of variousforms, functions, uses, end applications, etc.

If utilized, the compound can be present in the composition in variousamounts. The same is true for the copolymer if utilized in thecomposition. One of skill in the art can readily determine a suitableamount of the compound and/or the copolymer depending, for example, onthe particular composition, compound, or copolymer and the desiredoutcome.

In various embodiments, the composition is further defined as at leastone of: (i) an emulsion; (ii) an aqueous composition; (iii) a surfactantcomposition; (iv) a wetting composition; (v) an aqueous film-formingfoam; (vi) a surface tension modifier; (vii) an antiblocking additive;(viii) an agricultural composition; (ix) a coating composition; (x) apaint composition; (xi) a surface treating composition; (xii) afilm-forming composition; and (xiii) a cosmetic composition. One ofskill in the art appreciates that certain compositions may overlap as toform and/or function. Reference to the composition and any one of thesespecific compositions, e.g. the emulsion, may be interchangeable in thedescription that follows.

The compound can be used for numerous applications. In variousembodiments, the compound is used as at least one of a surfactant, adispersant, a wetting agent, an antiblocking additive, a surface tensionmodifier, a surface treating agent, an additive for agriculturalcompositions, an additive for coatings, an additive for paints, acosmetic ingredient, a siloxane modifier, and an aqueous film-formingfoam ingredient. One of skill in the art appreciates that certain usesor applications may overlap as to function and/or desired outcome.

The copolymer can also be used for numerous applications, with suchapplications being the same as or different from the uses describedabove for the compound. In certain embodiments, the copolymer is used asat least one of a surface treating agent, an additive for paints, anadditive for coatings, and a cosmetic ingredient.

In the composition, the compound or copolymer may be used alone ortogether, may be supplemented by at least one auxiliary component, ormay act as an auxiliary to at least one other component, optionally inthe presence of one of more additives. In various embodiments, thecompound or copolymer may be referred to as an agent, an additive, anadjuvant, an ingredient, or a modifier.

Each of the compound or copolymer may react with—or be inert withrespect to—other components present in the composition. In compositionsor applications where the composition, compound, or copolymer contacts asurface or substrate, there may be bonding to the surface or substrate,with such bonding being mechanical/physical, chemical, or a combinationthereof. For example, a surface may have functional groups that arereactive with the compound. Such functional groups may be inherent tothe surface or may be imparted by one or more types of conventionalsurface treatment. Certain exemplary compositions and components thereofare described below.

It is to be appreciated that certain components or additives may beclassified under different terms of art and just because a component oradditive is classified under such a term does not mean that they arelimited to that function. One or more of the additives can be present asany suitable weight percent (wt. %) of the composition, such as about0.01 wt. % to about 65 wt. %, about 0.05 wt. % to about 35 wt. %, about0.1 wt. % to about 15 wt. %, about 0.5 wt. % to about 5 wt. %, or about0.1 wt. % or less, about 1 wt. %, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, or about 15 wt. % or more of the composition. One of skill inthe art can readily determine a suitable amount of additive depending,for example, on the type of additive and the desired outcome. Certainoptional additives are described in greater detail below.

In various embodiments, the composition comprises or is an emulsion. Theemulsion is without limitation, and is generally selected from the groupof silicone/oil-in-water (O/W) and water-in-oil/silicone (W/O)emulsions. The emulsion comprises a non-aqueous phase and an aqueousphase. Typically, the non-aqueous phase is a discontinuous phase in theemulsion, and the aqueous phase is a continuous phase. However, thenon-aqueous phase may be the continuous phase, with the aqueous phasebeing the discontinuous phase, based on the relevant amounts ofcomponents therein, as described below.

The discontinuous phase generally forms particles in the continuousphase of the emulsion. The particles are liquid and may alternatively bereferred to as droplets. The size of the particles is typicallycontingent on, for example, the selection of components therein andtheir amounts.

In various embodiments, the non-aqueous phase of the emulsion comprisesthe compound and/or copolymer of this disclosure. In certainembodiments, the non-aqueous phase further comprises a carrier vehiclefor the compound and/or copolymer. The carrier vehicle may be selectedfrom vehicles understood in the art, such as siloxane carrier vehicles,inorganic and organic solvents, etc. In other or further embodiments,the non-aqueous phase further comprises a surfactant, as describedfurther below. Exemplary emulsions, compositions comprising emulsions,and films formed therewith, are described in WO2018145069A1.

Representative non-limiting examples of organic solvents includetoluene, xylene, and similar aromatic hydrocarbons; hexane, heptane,isooctane, and similar linear or partially branched saturatedhydrocarbons; cyclohexane and similar aliphatic hydrocarbons; lowmolecular weight alcohols such as methanol, ethanol, propanol,isopropanol and the like; low molecular weight ethers such asdi(propyleneglycol) mono methyl ether, di(ethyleneglycol) butyl ether,di(ethyleneglycol) methyl ether, di(propyleneglycol) butyl ether,di(propyleneglycol) methyl ether acetate, di(propyleneglycol) propylether, ethylene glycol phenyl ether, propylene glycol butyl ether,1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, propylene glycolpropyl ether, 1-phenoxy-2-propanol, tri(propyleneglycol) methyl etherand tri(propyleneglycol) butyl ether, and other like glycols.

The aqueous phase comprises water. The water may be from any source andmay optionally be purified, e.g. through filtration, distillation,reverse-osmosis techniques, etc.

In many embodiments, the emulsion further comprises a surfactant. Thesurfactant may alternatively be referred to as an emulsifier andgenerally serves to emulsify the non-aqueous phase in the aqueous phaseof the emulsion. The surfactant may be any surfactant suitable forpreparing the emulsion with the non-aqueous phase and the aqueous phase.

For example, the surfactant may comprise one or more anionic, cationic,nonionic, and/or amphoteric surfactants, organomodified silicones suchas dimethicone copolyol, oxyethylenated and/or oxypropylenated ethers ofglycerol, oxyethylenated and/or oxypropylenated ethers of fatty alcoholssuch as ceteareth-30, C12-15 pareth-7, fatty acid esters of polyethyleneglycol such as PEG-50 stearate, PEG-40 monostearate, saccharide estersand ethers such as sucrose stearate, sucrose cocoate and sorbitanstearate, and mixtures thereof, phosphoric esters and salts thereof suchas DEA oleth-10 phosphate, sulphosuccinates such as disodium PEG-5citrate lauryl sulphosuccinate and disodium ricinoleamido MEAsulphosuccinate, alkyl ether sulphates such as sodium lauryl ethersulphate, isethionates, betaine derivatives, and mixtures thereof.

In certain embodiments, the surfactant comprises the anionic surfactant.Anionic surfactants include, for example, carboxylates (sodium2-(2-hydroxyalkyloxy)acetate)), amino acid derivatives(N-acylglutamates, N-acylgly-cinates or acylsarcosinates), alkylsulfates, alkyl ether sulfates and oxyethylenated derivatives thereof,sulfonates, isethionates and N-acylisethionates, taurates and N-acylN-methyltaurates, sulfosuccinates, alkylsulfoacetates, phosphates andalkyl phosphates, polypeptides, anionic derivatives of alkylpolyglycoside (acyl-D-galactoside uronate), and fatty acid soaps, alkalimetal sulforicinates, sulfonated glyceryl esters of fatty acids such assulfonated monoglycerides of coconut oil acids, salts of sulfonatedmonovalent alcohol esters such as sodium oleylisethianate, amides ofamino sulfonic acids such as the sodium salt of oleyl methyl tauride,sulfonated products of fatty acids nitriles such as palmitonitrilesulfonate, sulfonated aromatic hydrocarbons such as sodiumalpha-naphthalene monosulfonate, condensation products of naphthalenesulfonic acids with formaldehyde, sodium octahydroanthracene sulfonate,alkali metal alkyl sulfates such as sodium lauryl sulfate, ammoniumlauryl sulfate and triethanol amine lauryl sulfate, ether sulfateshaving alkyl groups of 8 or more carbon atoms such as sodium laurylether sulfate, ammonium lauryl ether sulfate, sodium alkyl aryl ethersulfates, and ammonium alkyl aryl ether sulfates, alkylarylsulfonateshaving 1 or more alkyl groups of 8 or more carbon atoms,alkylbenzenesulfonic acid alkali metal salts exemplified byhexylbenzenesulfonic acid sodium salt, octylbenzenesulfonic acid sodiumsalt, decylbenzenesulfonic acid sodium salt, dodecylbenzenesulfonic acidsodium salt, cetylbenzenesulfonic acid sodium salt, andmyristylbenzenesulfonic acid sodium salt, sulfuric esters ofpolyoxyethylene alkyl ether including CH₃(CH₂)₆CH₂O(C₂H₄O)₂SO₃H,CH₃(CH₂)₇CH₂O(C₂H₄O)_(3.5)SO₃H, CH₃(CH₂)₈CH₂O(C₂H₄O)₈SO₃H,CH₃(CH₂)₁₉CH₂O(C₂H₄O)₄SO₃H, and CH₃(CH₂)₁₀CH₂O(C₂H₄O)₆SO₃H, sodiumsalts, potassium salts, and amine salts of alkylnaphthylsulfonic acid,and mixtures thereof.

In these or other embodiments, the surfactant comprises the cationicsurfactant. Cationic surfactants include, for example, various fattyacid amines and amides and their derivatives, and the salts of the fattyacid amines and amides. Examples of aliphatic fatty acid amines includedodecylamine acetate, octadecylamine acetate, and acetates of the aminesof tallow fatty acids, homologues of aromatic amines having fatty acidssuch as dodecylanalin, fatty amides derived from aliphatic diamines suchas undecylimidazoline, fatty amides derived from aliphatic diamines suchasundecylimidazoline, fatty amides derived from disubstituted aminessuch as oleylaminodiethylamine, derivatives of ethylene diamine,quaternary ammonium compounds and their salts which are exemplified bytallow trimethyl ammonium chloride, dioctadecyldimethyl ammoniumchloride, didodecyldimethyl ammonium chloride, dihexadecyl ammoniumchloride, alkyltrimethylammonium hydroxides such asoctyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide,and hexadecyltrimethylammonium hydroxide, dialkyldimethylammoniumhydroxides such as octyldimethylammonium hydroxide,decyldimethylammonium hydroxide, didodecyldimethylammonium hydroxide,dioctadecyldimethylammonium hydroxide, tallow trimethylammoniumhydroxide, coconut oil, trimethylammonium hydroxide,methylpolyoxyethylene cocoammonium chloride, anddipalmitylhydroxyethylammonium methosulfate, amide derivatives of aminoalcohols such as beta-hydroxylethylstearylamide, amine salts of longchain fatty acids, and mixtures thereof.

In these or other embodiments, the surfactant comprises the nonionicsurfactant. Nonionic surfactants include, for example, polyoxyethylenealkyl ethers (such as, lauryl, cetyl, stearyl or octyl), polyoxyethylenealkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylenesorbitan monoleates, polyoxyethylene alkyl esters, polyoxyethylenesorbitan alkyl esters, polyethylene glycol, polypropylene glycol,diethylene glycol, ethoxylated trimethylnonanols, polyoxyalkylene glycolmodified polysiloxane surfactants, polyoxyalkylene-substituted silicones(rake or ABn types), silicone alkanolamides, silicone esters, siliconeglycosides, dimethicone copolyols, fatty acid esters of polyols, forinstance sorbitol and glyceryl mono-, di-, tri- and sesqui-oleates andstearates, glyceryl and polyethylene glycol laurates; fatty acid estersof polyethylene glycol (such as polyethylene glycol monostearates andmonolaurates), polyoxyethylenated fatty acid esters (such as stearatesand oleates) of sorbitol, and mixtures thereof.

In these or other embodiments, the surfactant comprises the amophotericsurfactant. Amphoteric surfactants, include, for example, amino acidsurfactants, betaine acid surfactants, trimethylnonyl polyethyleneglycol ethers and polyethylene glycol ether alcohols containing linearalkyl groups having from 11 to 15 carbon atoms, such as2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (6 EO) (sold asTergitol®TMN-6 by OSi Specialties, A Witco Company, Endicott, N.Y.),2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (10 EO) (sold asTergitol®TMN-10 by OSi Specialties, A Witco Company, Endicott, N.Y.),alkylene-oxypolyethylene oxyethanol (C₁₁₋₁₅ secondary alkyl, 9 EO) (soldas Tergitol®15-S-9 by OSi Specialties, A Witco Company, Endicott, N.Y.),alkylene-oxypolyethylene oxyethanol (C₁₁₋₁₅ secondary alkyl, 15 EO)(sold as Tergitol®15-S-15 by OSi Specialties, A Witco Company, Endicott,N.Y.), octylphenoxy polyethoxy ethanols having varying amounts ofethylene oxide units such as octylphenoxy polyethoxy ethanol (40 EO)(sold as Triton® X405 by Rohm and Haas Company, Philadelphia, Pa.),nonionic ethoxylated tridecyl ethers available from Emery Industries,Mauldin, S.C. under the general tradename Trycol, alkali metal salts ofdialkyl sulfosuccinates available from American Cyanamid Company, Wayne,N.J. under the general tradename Aerosol, polyethoxylated quaternaryammonium salts and ethylene oxide condensation products of the primaryfatty amines (available from Armak Company, Chicago, Ilinois under thetradenames Ethoquad, Ethomeen, or Arquad), polyoxyalkylene glycolmodified polysiloxanes, N-alkylamidobetaines and derivatives thereof,proteins and derivatives thereof, glycine derivatives, sultaines, alkylpolyaminocarboxylates and alkylamphoacetates, and mixtures thereof.These surfactants may also be obtained from other suppliers underdifferent tradenames.

The surfactant may be included in the emulsion at concentrationseffective for emulsifying the non-aqueous phase in the aqueous phase (orvice versa). Such concentrations range from greater than 0 to 10,alternatively from 0.3 to 5, weight percent based on the total weight ofthe emulsion. The surfactant, or combination of surfactants, may bepresent in the aqueous phase of the emulsion, the non-aqueous phase ofthe emulsion, an interface of the aqueous and non-aqueous phases, orcombinations thereof.

The emulsion may further comprise one or more various optionaladditives, such as coupling agents, antistatic agents, ultraviolet (UV)absorbers, plasticizers, leveling agents, preservatives, surface activematerials (surfactants or detergents or emulsifiers), foam boosters,deposition agents, thickeners, water phase stabilizing agents, fillers,suspending agents, biocides, freeze/thaw additives, anti-freeze agents,viscosity modifiers, foam control agents, dyestuff (e.g. pigments),binders and combinations thereof.

Alternatively or in addition to the above, the emulsion may furthercomprise various additive compounds for improving properties of the filmformed therefrom. Examples of additive compounds are silanes, such astetrakis(dimethylamine)silane, tetraethylorthosilicate,glycidoxypropyltrimethoxysilane, triethylsilane,isobutyltrimethoxysilane; and siloxanes, such as heptamethyltrisiloxane,tetramethyldisloxane, etc.

In some embodiments, the emulsion is a coating composition, or may beformulated into a coating composition. Such coating compositions aretypically utilized to provide a continuous protective coating on asubstrate by applying the coating composition to a surface of thesubstrate. Examples of such substrates include organic or inorganiccomponents, and may include household materials such as leathers,papers, woods, metals, plastics, fabrics, paints, and the like. Thecoating compositions may also be suitable for use in other applicationsas well, e.g. as a protective and/or decorative coating, as a componentin a paint, etc.

In various embodiments, the compound and/or copolymer can be used asadditives for epoxy coatings. Numerous epoxy coatings are understood inthe art, including those described in U.S. Pat. No. 8,722,148 andUS20060205861.

In various embodiments, the composition comprises the emulsion and anorganic binder. The emulsion can be formed in situ in the composition,or the emulsion can be first prepared and then combined with the organicbinder, along with any other optional components, to give thecomposition. In certain embodiments, the composition is formed bycombining the emulsion and the organic binder, along with any optionalcomponents. The emulsion typically is present in the composition, i.e.,forming the composition with the emulsion doesn't destroy the emulsion.

The organic binder is not limited and is generally selected based on enduse applications of the composition. While exemplary examples are setforth below, any organic binder may be utilized in the composition. Theorganic binder may be reactive or non-reactive, and may be athermoplastic and/or thermoset. Typically, the organic binder is anorganic polymer and/or resin.

In certain embodiments, the organic binder comprises a natural latex. Inthese or other embodiments, the organic binder comprises a syntheticlatex. The organic binder may also be a combination of natural andsynthetic latex. For example, the organic binder is typically a naturaland/or synthetic latex when the composition is utilized to prepare filmsor paints. Natural and synthetic latexes are known in the art. Forexample, depending on a selection of the organic binder, the compositionmay be utilized as a paint, e.g. a heat resistant paint, which may besolventless. The paint may be utilized in insulation applications,anti-fouling applications, architectural applications,commercial/industrial or residential applications, protectiveapplications, leather applications, textile applications, etc.

Specific examples of organic binders include, but are not limited to,polyolefins, acrylic polymers, polyvinyl acetate, polyvinyl chloride,styrenes (e.g. styrene-butadiene rubber), acrylonitrile-butadienes,epoxy resins, phenolics, polyesters, polyvinylbutyral, phenoxys,polyureas, cellulosic resins, polyurethanes, polyamides, polyethers,alkyds, silicones, acrylonitriles, etc. The organic binder may comprisea combination of such organic binders, or copolymers or terpolymersincluding one or more such organic binders.

The content of the organic binder in the composition may vary on anumber of factors, such as its selection, the type and amount of theemulsion present in the composition, end use applications of thecomposition, etc. Increased loadings of the organic binder generallyresult in films having greater hardness and other increased physicalproperties. In certain embodiments, the composition comprises the binderin an amount of from greater than 0 to less than 100, alternatively fromgreater than 0 to 50, alternatively from 0.1 to 40, alternatively from 5to 15, wt. % based on the total weight of the composition.

The organic binder may be dispersed or disposed in a carrier vehicle.The carrier vehicle may be any suitable carrier vehicle, which typicallysolubilizes the organic binder. The carrier vehicle is typically afunction of the organic binder utilized. The carrier vehicle may bewater such that the composition as a whole is water-based, or may be asolvent other than water, e.g. an organic solvent. In certainembodiments, like the emulsion, the composition is substantially freefrom water. Substantially free from water is defined with respect to theemulsion.

In some embodiments the composition further comprises one or moreoptional components. The composition may comprise any of the optionalcomponents described above with respect to the emulsion. These optionalcomponents may be included in the composition from being present in theemulsion, may be incorporated into the composition independent from theemulsion, or both. Specific examples of optional components include, butare not limited to, colorants, coalescing aids, surfactants, thickeners,defoamers, compatibilizers, UV stabilizers, antioxidants, biocides,flame retardants, etc., Some of these optional components may be presentin the emulsion, as described above, and thus included in thecomposition, or one or more of these optional components may beincorporated when forming the composition. Any of the optionalcomponents described above relative to the emulsion may also be presentin the composition, either through introduction from the emulsion orfrom inclusion of an additional amount of the particular component. Byway of example, the composition may comprise a catalyst, which may bethe same as or different from any catalyst that may be present in theemulsion.

In certain embodiments, the composition further comprises one or morecolorants, such as pigments, dyes, and the like. Such colorants can beorganic or inorganic, synthetic or natural. Examples of colorants areset forth above regarding the emulsion. The emulsion and the compositionitself may include different colorants which are independently selected.Additional examples of suitable colorants include cadmium yellow,cadmium red, cadmium green, cadmium orange, carbon black (including vineblack, lamp black), ivory black (bone char), chrome yellow, chromegreen, cobalt violet, cobalt blue, cerulean blue, aureolin (cobaltyellow), Azurite, Han purple, Han blue, Egyptian blue, Malachite, Parisgreen, Phthalocyanine Blue BN, Phthalocyanine Green G, verdigris,viridian, sanguine, caput mortuum, oxide red, red ochre, Venetian red,Prussian blue, yellow ochre, raw sienna, burnt sienna, raw umber, burntumber, Cremnitz white, Naples yellow, vermilion titanium yellow,titanium beige, titanium white (TiO₂), titanium black, ultramarine,ultramarine green shade, zinc white, zinc ferrite, alizarin (synthesizedor natural), alizarin crimson (synthesized or natural), gamboge,cochineal red, rose madder, indigo, Indian yellow, Tyrian purple,quinacridone, magenta, phthalo green, phthalo blue, pigment red 170, orany combinations thereof.

In particular embodiments, the composition further comprises acoalescing aid. Suitable coalescing aids include any compound thatdecreases the minimum film-formation temperature of the organic binder,when the organic binder indeed forms a film, and/or increases the rateof solid film formation from the organic binder when any carrier vehicleor water is removed from the composition. Examples of suitablecoalescing aids include glycol ethers, 2,2,4-trimethyl-1,3-pentanediolisobutyrate, and combinations thereof

In certain embodiments, the composition comprises a surfactant. Thesurfactant may be the same as or different from any surfactant utilizedin the emulsion, examples of which are set forth above.

Thickeners (or rheology modifiers) may also be included in thecomposition to achieve desired viscosity and flow properties. Dependingon their selection, as the selection of the organic binder, thethickeners may function by, for example, forming multiple hydrogen bondswith the organic binder, thereby causing chain entanglement, loopingand/or swelling which results in volume restriction. In certainembodiments, thickeners such as cellulose derivatives includinghydroxyethyl cellulose, methyl cellulose and carboxymethyl cellulose,may be utilized.

In some embodiments, the composition includes a defoamer. The defoamermay be any suitable chemical additive that reduces and hinders theformation of foam in the composition. Defoamers are known in the art andare typically selected based on other components present in thecomposition.

When the composition comprises the compatibilizer, the compatibilizermay be any compound or component which modifies, alternatively improves,the wetting of the components in the composition. Examples of suchcompatibilizers include titanium alcoholates, esters of phosphoric,phosphorous, phosphonic, and silicic acids, metallic salts and esters ofaliphatic, aromatic, and cycloaliphatic acids, ethylene/acrylic ormethacrylic acids, ethylene/esters of acrylic or methacrylic acid,ethylene/vinyl acetate resins, styrene/maleic anhydride resins or estersthereof, acrylonitrilebutadiene styrene resins, methacrylate/butadienestyrene resins (MBS), styrene acrylonitrile resins (SAN), andbutadieneacrylonitrile copolymers. Alternatively or in addition, thecompatibilizer may comprise a silane, e.g. a hydrocarbonoxysilane suchas an alkoxysilane, a combination of an alkoxysilane and ahydroxy-functional polyorganosiloxane, an aminofunctional silane, or acombination thereof. The silane may include any functional group, whichmay be an adhesion-promoting group, such as amino, epoxy, mercaptoand/or acrylate groups. Combinations of functional groups may beutilized, e.g. the (D) compatibilizer may comprise an epoxy-functionalalkoxysilane. Suitable epoxy-functional organic groups are exemplifiedby 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. Unsaturated organicgroups are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl,and unsaturated monovalent hydrocarbon groups such as vinyl, allyl,hexenyl, undecylenyl. Examples of suitable epoxy-functionalalkoxysilanes include 3-glycidoxypropyltrim ethoxysilane,3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane,(epoxycyclohexyl)ethyldiethoxysilane and combinations thereof. Examplesof suitable unsaturated alkoxysilanes include vinyltrimethoxysilane,allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane,undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane,3-methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyl triethoxysilane, and combinationsthereof. Aminofunctional silanes, such as an aminofunctionalalkoxysilanes, may have various amino groups, as understood in the art.Other examples of compatibilizers include modified polyethylene andmodified polypropylene, which are obtained by modifying polyethylene andpolypropylene, respectively, using a reactive group, including polarmonomers such as maleic anhydride or esters, acrylic or methacrylic acidor esters, vinylacetate, acrylonitrile, and styrene.

Specific examples of UV stabilizers include phenol,2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-, branched and linear(TINUVIN® 571). Additional examples of suitable UV stabilizers includebis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate; methylI,2,2,6,6-pentamethyl-4-piperidyl/sebacate; and a combination thereof(TINUVIN® 272). These and other TINUVIN® additives, such as TINUVIN® 765are commercially available from Ciba Specialty Chemicals of Tarrytown,N.Y., U.S.A. Other UV and light stabilizers are commercially available,and are exemplified by LowLite from Chemtura, OnCap from PolyOne, andLight Stabilizer 210 from E. I. du Pont de Nemours and Company ofDelaware, U.S.A. An example of an oligomeric antioxidant stabilizer(specifically, hindered amine light stabilizer (HALS)) is Ciba TINUVIN®622, which is a dimethylester of butanedioic acid copolymerized with4-hydroxy-2,2,6,6-tetramethyl-I-piperidine ethanol.

If utilized, the antioxidant may be any antioxidant known in the art.Specific examples thereof include phenolic antioxidants and combinationsof phenolic antioxidants with stabilizers. Phenolic antioxidants includefully sterically hindered phenols and partially hindered phenols; andsterically hindered amines such as tetramethyl-piperidine derivatives.Suitable phenolic antioxidants include vitamin E and IRGANOX® 1010 fromCiba Specialty Chemicals, U.S.A. IRGANOX® 1010 comprises pentaerythritoltetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate). Additionalexamples of antioxidants are acetyl cysteine, arbutin, ascorbic acid,ascorbic acid polypeptide, ascorbyl dipalmitate, ascorbyl methylsilanolpectinate, ascorbyl palmitate, ascorbyl stearate, BHA, p-hydroxyanisole,BHT, t-butyl hydroquinone, caffeic acid, Camellia sinensis oil, chitosanascorbate, chitosan glycolate, chitosan salicylate, chlorogenic acids,cysteine, cysteine HCl, decyl mercaptomethylimidazole, erythorbic acid,diamylhydroquinone, di-t-butylhydroquinone, dicetyl thiodipropionate,dicyclopentadiene/t-butylcresol copolymer, digalloyl trioleate, dilaurylthiodipropionate, dimyristyl thiodipropionate, dioleyl tocopherylmethylsilanol, isoquercitrin, diosmine, disodium ascorbyl sulfate,disodium rutinyl disulfate, distearyl thiodipropionate, ditridecylthiodipropionate, dodecyl gallate, ethyl ferulate, ferulic acid,hydroquinone, hydroxylamine HCl, hydroxylamine sulfate, isooctylthioglycolate, kojic acid, madecassicoside, magnesium ascorbate,magnesium ascorbyl phosphate, melatonin, methoxy-PEG-7 rutinylsuccinate, methylene di-t-butylcresol, methylsilanol ascorbate,nordihydroguaiaretic acid, octyl gallate, phenylthioglycolic acid,phloroglucinol, potassium ascorbyl tocopheryl phosphate,thiodiglycolamide, potassium sulfite, propyl gallate, rosmarinic acid,rutin, sodium ascorbate, sodium ascorbyl/cholesteryl phosphate, sodiumbisulfite, sodium erythorbate, sodium metabisulfide, sodium sulfite,sodium thioglycolate, sorbityl furfural, tea tree (Melaleucaaftemifolia) oil, tocopheryl acetate, tetrahexyldecyl ascorbate,tetrahydrodiferuloylmethane, tocopheryl linoleate/oleate, thiodiglycol,tocopheryl succinate, thiodiglycolic acid, thioglycolic acid, thiolacticacid, thiosalicylic acid, thiotaurine, retinol, tocophereth-5,tocophereth-10, tocophereth-12, tocophereth-18, tocophereth-50,tocopherol, tocophersolan, tocopheryl linoleate, tocopheryl nicotinate,tocoquinone, o-tolyl biguanide, tris(nonylphenyl) phosphite, ubiquinone,zinc dibutyldithiocarbamate, and mixtures thereof.

Biocides may be exemplified by fungicides, herbicides, pesticides,antimicrobial agents, or a combination thereof.

Specific examples of fungicides include N-substituted benzimidazolecarbamate, benzimidazolyl carbamate such as methyl2-benzimidazolylcarbamate, ethyl 2-benzimidazolylcarbamate, isopropyl2-benzimidazolylcarbamate, methylN-{2-[I-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, methylN-{2-[I-(N,N-dimethylcarbamoyl)-6-methylbenzimidazolyl]}carbamate,methylN-{2-[I-(N,N-dimethylcarbamoyl)-5-methylbenzimidazolyl]}carbamate,methyl N-{2-[I-(N-methylcarbamoyl)benzimidazolyl]}carbamate, methylN-{2-[I-(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, methylN-{2-[I-(N-methylcarbamoyl)-5-methylbenzimidazolyl]}carbamate, ethylN-{2-[I-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, ethylN-{2-[2-(N-methylcarbamoyl)benzimidazolyl]}carbamate, ethylN-{2-[I-(N,N-dimethylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, ethylN-{2-[I-(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, isopropylN-{2-[I-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, isopropylN-{2-[I-(N-methylcarbamoyl)benzimidazolyl]}carbamate, methylN-{2-[I-(N-prop ylcarbamoyl)benzimidazolyl]}carbamate, methylN-{2-[I-(N-butylcarbamoyl)benzimidazolyl]}carbamate, methoxyethylN-{2-[I-(N-prop ylcarbamoyl)benzimidazolyl]}carbamate, methoxyethylN-{2-[I-(N-butylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethylN-{2-[I-(N-prop ylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethylN-{2-[I-(N-butylcarbamoyl)benzimidazolyl]}carbamate, methylN-{1-(N,N-dimethylcarbamoyloxy)benzimidazolyl]}carbamate, methylN-{2-[N-methylcarbamoyloxy)benzimidazolyl]}carbamate, methylN-{2-[I-(N-butylcarbamoyloxy)benzoimidazolyl]}carbamate, ethoxyethylN-{2-[I-(N-prop ylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethylN-{2-[I-(N-butylcarbamoyloxy)benzoimidazolyl]}carbamate, methylN-{2-[I-(N,N-dimethylcarbamoyl)-6-chlorobenzimidazolyl]}carbamate, andmethyl N-{2-[I-(N,N-dimethylcarbamoyl)-6-nitrobenzimidazolyl]}carbamate;10, 10′-oxybisphenoxarsine (which has trade name Vinyzene, OB PA),di-iodomethyl-para-tolylsulfone,benzothiophene-2-cyclohexylcarboxamide-S,S-dioxide,N-(fluordichloridemethylthio)phthalimide (which has trade namesFluor-Folper, and Preventol A3); methyl-benzimideazol-2-ylcarbamate(which has trade names Carbendazim, and Preventol BCM), zinc-bis(2-pyridylthio-I-oxide) (zinc pyrithion) 2-(4-thiazolyl)-benzimidazol,N-phenyl-iodpropargylcarbamate, N-octyl-4-isothiazolin-3-on,4,5-dichloride-2-n-octyl-4-isothiazolin-3-on,N-butyl-1,2-benzisothiazolin-3-on and/or triazolyl-compounds, such astebuconazol in combination with zeolites containing silver.

Alternatively, the biocide may comprise a boron containing material,e.g., boric anhydride, borax, or disodium octaborate tetrahydrate; whichmay function as a pesticide, fungicide, and/or flame retardant.

Specific examples of suitable flame retardants include carbon black,hydrated aluminum hydroxide, and silicates such as wollastonite,platinum and platinum compounds. Alternatively, the flame retardant, ifutilized, may be selected from halogen based flame-retardants such asdecabromodiphenyloxide, octabromodiphenyl oxide, hexabromocyclododecane,decabromobiphenyl oxide, diphenyoxybenzene, ethylenebis-tetrabromophthalmide, pentabromoethyl benzene, pentabromobenzylacrylate, tribromophenyl maleic imide, tetrabromobisphenyl A,bis-(tribromophenoxy) ethane, bis-(pentabromophenoxy) ethane,polydibomophenylene oxide, tribromophenylallyl ether, bis-dibromopropylether, tetrabromophthalic anhydride, dibromoneopentyl gycol,dibromoethyl dibromocyclohexane, pentabromodiphenyl oxide,tribromostyrene, pentabromochlorocyclohexane, tetrabromoxylene,hexabromocyclododecane, brominated polystyrene,tetradecabromodiphenoxybenzene, trifluoropropene and PVC. Alternatively,the flame retardant, if utilized, may be selected from phosphorus basedflame-retardants such as (2,3-dibromopropyl)-phosphate, phosphorus,cyclic phosphates, triaryl phosphate, bis-melaminium pentate,pentaerythritol bicyclic phosphate, dimethyl methyl phosphate, phosphineoxide diol, triphenyl phosphate, tris-(2-chloroethyl) phosphate,phosphate esters such as tricreyl, trixylenyl, isodecyl diphenyl,ethylhexyl diphenyl, phosphate salts of various amines such as ammoniumphosphate, trioctyl, tributyl or tris-butoxyethyl phosphate ester. Othersuitable flame retardants may include tetraalkyl lead compounds such astetraethyl lead, iron pentacarbonyl, manganese methyl cyclopentadienyltricarbonyl, melamine and derivatives such as melamine salts, guanidine,dicyandiamide, ammonium sulphamate, alumina trihydrate, and magnesiumhydroxide alumina trihydrate.

Aqueous compositions include any composition that includes water as acomponent, generally as a primary or majority component (e.g. as asolvent, carrier or medium). In these embodiments, the aqueouscomposition further comprises the compound and/or copolymer of thisdisclosure.

As understood in the art, surfactants are compounds that lower thesurface tension (or interfacial tension) between two liquids, between agas and a liquid, or between a liquid and a solid. Surfactants may actas detergents, wetting agents, emulsifiers, foaming agents, anddispersants. Surfactants can serve as cleaning, wetting, dispersing,emulsifying, foaming and anti-foaming agents in many practicalapplications and products, including, but not limited to, detergents,fabric softeners, emulsions, soaps, paints, adhesives, inks, anti-fogs,ski waxes, snowboard wax, deinking of recycled papers, in flotation,washing and enzymatic processes, laxatives, etc. Agrochemicalformulations such as some herbicides, insecticides, biocides(sanitizers), and spermicides may also include one or more surfactants.Personal care products such as cosmetics, shampoos, shower gel, hairconditioners (after shampoo), and toothpastes often include one or moresurfactants.

In various embodiments, the surfactant composition comprises thecompound and/or copolymer of this disclosure. In certain embodiments,the surfactant composition further comprises one or more additivesunderstood in the art, such as water and/or other vehicles, one or moreconventional surfactants, etc. One of skill in the art appreciates thatsurfactant compositions may also be referred to as wetting compositions,surface tension modifiers, or dispersant compositions. In someapplications, there may be slight nuances as to differences in form,function, and/or end application of such compositions.

In other embodiments, the compound itself—and/or the copolymer itself—isa surfactant. In these embodiments, the compound and/or copolymer may bereferred to as a dispersant, a wetting agent, or a surface tensionmodifier.

In various embodiments, the composition is selected from the groupconsisting of film-forming compositions, including foaming andsubstantially non-foaming compositions, aqueous and non-aqueouscompositions, and combinations thereof. Certain films are describedbelow. The composition may be curable, partially curable, or may notcure. In embodiments where the composition is at least partially curableto curable, the composition can change form, such as going from a liquidto a more viscous liquid, a gel, a semi-solid, or a solid.

In various embodiments, the composition is useful as an antiblocking (oranti-blocking) additive (or agent). In these embodiments, thecomposition may also provide scratch resistance and a low coefficient offriction (COF). In certain embodiments, the compound itself—and/or thecopolymer itself—is the antiblocking additive.

Antiblocking agents are often used in or for films, e.g. in polyolefinfilms, to improve the slippage among individual molecules of theantiblocking agent and are important ingredients for the post-processingconversion (cutting, folding, welding etc.) of such films. Blocking is acommon problem encountered by manufacturers of films and coatings.Blocking is the adhesion of two adjacent layers of film. It is a problemmost associated with polyethylene and polypropylene films (either blownor cast) and to a lesser extent in extrusion coated or laminatedproducts. Blocking of adjacent film layers occurs due to the presence ofvan der Waals forces between the amorphous regions of the polymer. Theseforces increase with reduced distance between the two layers, therebyincreasing blocking when two layers are pressed together (e.g. bindingonto a take up roll or stacking of finished, converted films). Anotherpossible reason for blocking is the presence of low molecular weightspecies (such as oligomers) which tend to migrate to the surface of thefilm.

An effective method for combating these handling problems is to add anantiblocking additive. An antiblocking additive present in the resinmicroscopically protrudes from the film surface. This creates asperities(“little bumps”) which help to minimize the film-to-film surfacecontact, increasing the distance between the two layers, therebyminimizing blocking.

The blocking between adjacent layers results in increased friction andthe addition of an antiblocking agent generally contributes to areduction in the film-to-film COF. COF is a measure of the relativedifficulty with which one surface will slide over an adjoining surface.The greater the resistance to sliding, the higher the COF value (e.g.“low-slip” or “no-slip” films, sometimes referred to as “high COF”films).

In various embodiments, the composition is an agricultural composition.At least one of the compound and copolymer can be used as an additivefor the agricultural composition. Numerous types of compositions forfacilitating agriculture are understood in the art, including those thatpromote plant grown, control or prevent weeds, control or preventvarmints and insects, etc. Whether using a plant growth regulator or agenetically altered plant, any number of agronomically suitableadditives, adjuvants and/or phytocatalysts are applied to the plants tosupport or enhance plant growth, including: fertilizers containingelements such as nitrogen, phosphorus, potassium, elevated carbondioxide, hydrogen peroxide, iron and manganese; secondary nutrients suchas sources of sulfur, calcium, and magnesium; micronutrients, such asboron, cobalt, copper, molybdenum, zinc, nickel; water solublecarbohydrates such as sucrose, fructose and glucose; and various alkylglucosides.

In various embodiments, the composition includes at least one pesticide.The term pesticide is understood to encompass herbicides, insecticides,acaricides, nematicides, ectoparasiticides, fungicides and plant growthregulators. The composition is not limited in this regard.

Examples of classes of compounds that have herbicidal activity includeimidazolinones such as imazaquin, sulfonylureas such aschlorimuron-ethyl, triazolopyrimidine sulfonamides such as flumetsulam,aryloxyphenoxy propionates such as quizalofop ethyl, aryl ureas such asisoproturon and chlorotoluron, triazines such as atrazine and simazine,aryl carboxylic acids such as picloram, aryloxy alkanoic acids such asMCPA, chloroacetanilides such as metazachlor, dintroanilines such asoryzalin, pyrazoles such as pyrazolynate and diphenyl ethers such asbifenox. Examples of classes of compounds that have insecticidalactivity include benzoyl ureas such as hexaflumuron, diacylhydrazinessuch as tebufenozide, carbamates such as carbofuran, pyrethroids such ascypermethrin, organophosphates such as phosmet, triazoles, and naturalproducts such as spinosyns.

Examples of classes of compounds that have fungicidal activity includemorpholines such as dimethomorph, phenylamides such as benalaxyl, azolessuch as hexaconazole, strobilurins such as azoxystrobin, phthalonitrilessuch as chlorothalonil and phenoxyquinolines such as quinoxyfen.

Examples of insecticides/acaricides are benthiocarb, diflubenzuron,teflubenzuron, lufenuron, diafenthiuron or pyrethroide such asbifenthrin, bioallethrin, tau-fluvalinate, resmethrin, permethrin,cypermethrin, cyfluthrin, cyhalothrin, deltamethrin, tefluthrin ortetramethrin; furtheron pymetrozin, thiocyclam, fenoxycarb, methopren,abamectin and emamectin.

In various embodiments, the compound and/or copolymer can be used fortreatment of particles, for example, as intermediates to treat metaloxide particle surfaces. The particles can be of various sizes andparticle size distributions, including nano- and micro-sized.

The metal oxide particles can be any suitable metal oxide particles.Suitable metal oxide particles include, for example, aluminum oxide,titanium oxide, silica, tin oxide, magnesium oxide, zinc oxide,strontium oxide particles, mixtures thereof, and co-oxides thereof.

The particles may be electrically and/or thermally conductive ornon-conductive. In certain embodiments, the particles are classified aselectrically conductive filler, which can be a metal or a conductivenon-metal; or metal or non-metal particles having an outer surface of ametal, with the outer surface metal being a noble metal such as silver,gold, platinum, palladium, and alloys thereof, or a base metal such asnickel, aluminum, copper, or steel. The particles can also have an outersurface of a metal with a core of particles consisting of copper, solidglass, hollow glass, mica, nickel, ceramic fiber or polymeric such aspolystyrene and polymethylmethacrylate.

In certain embodiments, the particles are classified as thermallyconductive filler, which can be a metal particle, metal oxide particle,thermally conductive non-metal powder, or combinations thereof. Thethermally conductive filler can be aluminum, copper, gold, nickel,silver, alumina, magnesium oxide, beryllium oxide, chromium oxide,titanium oxide, zinc oxide, barium titanate, diamond, graphite, carbonor silicon nano-sized particles, boron nitride, aluminum nitride, boroncarbide, titanium carbide, silicon carbide, and tungsten carbide.

Examples of mineral fillers or pigments which can be treated includetitanium dioxide, aluminium trihydroxide (also called ATH), magnesiumdihydroxide, mica, kaolin, calcium carbonate, non-hydrated, partiallyhydrated, or hydrated fluorides, chlorides, bromides, iodides,chromates, carbonates, hydroxides, phosphates, hydrogen phosphates,nitrates, oxides, and sulphates of sodium, potassium, magnesium,calcium, and barium; zinc oxide, aluminium oxide, antimony pentoxide,antimony trioxide, beryllium oxide, chromium oxide, iron oxide,lithopone, boric acid or a borate salt such as zinc borate, bariummetaborate or aluminium borate, mixed metal oxides such asaluminosilicate, vermiculite, silica including fumed silica, fusedsilica, precipitated silica, quartz, sand, and silica gel; rice hullash, ceramic and glass beads, zeolites, metals such as aluminium flakesor powder, bronze powder, copper, gold, molybdenum, nickel, silverpowder or flakes, stainless steel powder, tungsten, hydrous calciumsilicate, barium titanate, silica-carbon black composite, functionalizedcarbon nanotubes, cement, fly ash, slate flour, ceramic or glass beads,bentonite, clay, talc, anthracite, apatite, attapulgite, boron nitride,cristobalite, diatomaceous earth, dolomite, ferrite, feldspar, graphite,calcined kaolin, molybdenum disulfide, perlite, pumice, pyrophyllite,sepiolite, zinc stannate, zinc sulphide or wollastonite.

Other fillers which may be treated include natural fibres such as woodflour, wood fibres, cotton fibres or agricultural fibres such as wheatstraw, hemp, flax, kenaf, kapok, jute, ramie, sisal, henequen, cornfibre or coir, nut shells or rice hulls, lignin, starch, or celluloseand cellulose-containing products, or certain synthetic fibres such asaramid fibres, nylon fibres, cotton fibres or glass fibres, or plasticmicrospheres of polytetrafluoroethylene or polyethylene and theinvention includes treatment of such fillers. The filler can be a solidorganic pigment such as those incorporating azo, indigoid,triphenylmethane, anthraquinone, hydroquinone or xanthine dyes, or asolid organic flame retardant such as polychlorobiphenyl ordecabromodiphenyl oxide or a phosphorus-containing flame retardant.

In various embodiments, the compound and/or copolymer can be used tomodify a siloxane or composition comprising at least one siloxane. Themodification may be direct or indirect, such as in stances where thecompound may react with the siloxane. Additional embodiments of thecomposition are described below.

The composition may include one or more fillers. The fillers may be oneor more reinforcing fillers, non-reinforcing fillers, or mixturesthereof. Examples of finely divided, reinforcing fillers include highsurface area fumed and precipitated silicas including rice hull ash andto a degree calcium carbonate. Examples of finely dividednon-reinforcing fillers include crushed quartz, diatomaceous earths,barium sulphate, iron oxide, titanium dioxide and carbon black, talc,and wollastonite. Other fillers which might be used alone or in additionto the above include carbon nanotubes, e.g. multiwall carbon nanotubesaluminite, hollow glass spheres, calcium sulphate (anhydrite), gypsum,calcium sulphate, magnesium carbonate, clays such as kaolin, aluminumtrihydroxide, magnesium hydroxide (brucite), graphite, copper carbonate,e.g. malachite, nickel carbonate, e.g. zarachite, barium carbonate, e.g.witherite and/or strontium carbonate e.g. strontianite. Furtheralternative fillers include aluminum oxide, silicates from the groupconsisting of olivine group; garnet group; aluminosilicates; ringsilicates; chain silicates; and sheet silicates. In certain embodiments,the composition includes at least one filler comprising hollowparticles, e.g. hollow spheres. Such fillers can be useful forcontributing to porosity and/or overall void fraction of the foam. Incertain embodiments, some fillers can be utilized to tune thethixotropic property of the composition.

The filler if present, may optionally be surface treated with a treatingagent. Treating agents and treating methods are understood in the art.The surface treatment of the filler(s) is typically performed, forexample with a fatty acid or a fatty acid ester such as a stearate, orwith organosilanes, organosiloxanes, or organosilazanes such ashexaalkyi disilazane or short chain siloxane diols. Generally thesurface treatment renders the filler(s) hydrophobic and therefore easierto handle and obtain a homogeneous mixture with the other components inthe composition. Silanes such as R⁵ _(e)Si(OR⁶)_(4-e) where R⁵ is asubstituted or unsubstituted monovalent hydrocarbon group of 6 to 20carbon atoms, for example, alkyl groups such as hexyl, octyl, dodecyl,tetradecyl, hexadecyl, and octadecyl, and aralkyl groups such as benzyland phenylethyl, R⁶ is an alkyl group of 1 to 6 carbon atoms, andsubscript “e” is equal to 1, 2 or 3, may also be utilized as thetreating agent for fillers. In certain embodiments, at least one of thecompound and copolymer can used as a treating agent as described above,optionally in combination with one or more conventional treating agents.

In various embodiments, the composition further comprises a reactioninhibitor. For example, an alkyne alcohol such as 2-methyl-3-butyn-2-ol,3,5-dimethyl-1-hexyn-3-ol, or 2-phenyl-3-butyn-2-ol; an ene-yne compoundsuch as 3-methyl-3-penten-1-yne or 3,5-dimethyl-3-hexen-1-yne; or1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane,1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, or abenzotriazole may be incorporated as an optional component in thecomposition.

In various embodiments, the composition further comprises a thixotropicagent. Suitable thixotropic agents include rheological agents, specificexamples of such agents may be found in U.S. Pub. Nos. 2018/0066115 A1and 2018/0208797 A1.

In various embodiments, the composition further comprises anadhesion-imparting agent. The adhesion-imparting agent can improveadhesion of the foam to a base material being contacted during curing,e.g. the second surface 36. In certain embodiments, theadhesion-imparting agent is selected from organosilicon compounds havingat least one alkoxy group bonded to a silicon atom in a molecule. Thisalkoxy group is exemplified by a methoxy group, an ethoxy group, apropoxy group, a butoxy group, and a methoxyethoxy group. Moreover,non-alkoxy groups bonded to a silicon atom of this organosiliconcompound are exemplified by substituted or non-substituted monovalenthydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups,aralkyl groups, halogenated alkyl groups and the like; epoxygroup-containing monovalent organic groups such as a 3-glycidoxypropylgroup, a 4-glycidoxybutyl group, or similar glycidoxyalkyl groups; a2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propylgroup, or similar epoxycyclohexylalkyl groups; and a 4-oxiranylbutylgroup, an 8-oxiranyloctyl group, or similar oxiranylalkyl groups;acrylic group-containing monovalent organic groups such as a3-methacryloxypropyl group and the like; and a hydrogen atom.

This organosilicon compound generally has a silicon-bonded alkenyl groupor silicon-bonded hydrogen atom. Moreover, due to the ability to impartgood adhesion with respect to various types of base materials, thisorganosilicon compound generally has at least one epoxy group-containingmonovalent organic group in a molecule. This type of organosiliconcompound is exemplified by organosilane compounds, organosiloxaneoligomers and alkyl silicates. Molecular structure of the organosiloxaneoligomer or alkyl silicate is exemplified by a linear chain structure,partially branched linear chain structure, branched chain structure,ring-shaped structure, and net-shaped structure. A linear chainstructure, branched chain structure, and net-shaped structure aretypical. This type of organosilicon compound is exemplified by silanecompounds such as 3-glycidoxypropyltrimethoxysilane,2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like; siloxane compounds having at leastone silicon-bonded alkenyl group or silicon-bonded hydrogen atom, and atleast one silicon-bonded alkoxy group in a molecule; mixtures of asilane compound or siloxane compound having at least one silicon-bondedalkoxy group and a siloxane compound having at least one silicon-bondedhydroxy group and at least one silicon-bonded alkenyl group in themolecule; and methyl polysilicate, ethyl polysilicate, and epoxygroup-containing ethyl polysilicate.

In various embodiments, the composition includes at least one blowingagent. If utilized, the blowing agent can be selected from the group ofchemical blowing agents, physical blowing agents, and combinationsthereof. The amount of blowing agent utilized can vary depending on thedesired outcome. For example, the amount of blowing agent can be variedto tailor final foam density and foam rise profile.

The composition can include carrier vehicles (or diluents) includesilicones, both linear and cyclic, organic oils, organic solvents andmixtures of these. Specific examples of solvents may be found in U.S.Pat. No. 6,200,581. The carrier vehicle may also be a low viscosityorganopolysiloxane or a volatile methyl siloxane or a volatile ethylsiloxane or a volatile methyl ethyl siloxane having a viscosity at 25°C. in the range of 1 to 1,000 mm²/sec, such ashexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,ecamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,octamethyltrisiloxane, decamethyltetrasiloxane,dodecamethylpentasiloxane, tetradecamethylhexasiloxane,exadeamethylheptasiloxane,heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane,hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxanepentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane as well aspolydimethylsiloxanes, polyethylsiloxanes, polymethylethylsiloxanes,polymethylphenylsiloxanes, polydiphenylsiloxanes, caprylyl methicone,and any mixtures thereof.

In some embodiments, the composition comprises one or more additionalcomponents, such as a rheology modifier, a polar organic solvent, athickener, an inorganic salt (e.g. calcium chloride), a personal careactive/ingredient, a fragrance, or combinations thereof. Typically, theone or more additional components are selected based on a desired use ofthe composition. For example, in some embodiments the composition isformulated for use as a personal care composition and further comprisesa personal care ingredient. The specific personal care ingredient, or amixture of specific personal care ingredients, may be selected based onthe type of personal care composition the composition is beingformulated as. In these embodiments, the personal care ingredient may bea liquid, a solid, an encapsulated liquid, etc. Various examples of thepersonal care ingredient are described below. Any of these personal careingredients, or a combination of two or more different personal careingredients, may be utilized as the personal care ingredient. Forclarity and consistency, “the personal care ingredient” encompassesembodiments where the composition includes but one or two or morepersonal care ingredients.

In specific embodiments, the personal care ingredient is anantiperspirant and/or deodorant (AP/DEO) agent. In these embodiments,the composition may be referred to as an antiperspirant and/or deodorant(AP/DEO) composition. Examples of antiperspirant agents and deodorantagents include aluminum chloride, aluminum zirconium tetrachlorohydrexGLY, aluminum zirconium tetrachlorohydrex PEG, aluminum chlorohydrex,aluminum zirconium tetrachlorohydrex PG, aluminum chlorohydrex PEG,aluminum zirconium trichlorohydrate, aluminum chlorohydrex PG, aluminumzirconium trichlorohydrex GLY, hexachlorophene, benzalkonium chloride,aluminum sesquichlorohydrate, sodium bicarbonate, aluminumsesquichlorohydrex PEG, chlorophyllin-copper complex, triclosan,aluminum zirconium octachlorohydrate, zinc ricinoleate, and mixturesthereof.

In certain embodiments, the personal care ingredient comprises a skincare ingredient. If utilized to prepare the composition, the skin careingredient is typically selected from water phase stabilizing agents,cosmetic biocides, conditioning agents (which may be silicone, cationic,hydrophobic, etc.), emollients, moisturizers, colorants, dyes,ultraviolet (UV) absorbers, sunscreen agents, antioxidants, fragrances,antimicrobial agents, antibacterial agents, antifungal agents, antiagingactives, anti-acne agents, skin-lightening agents, pigments,preservatives, pH controlling agents, electrolytes, chelating agents,plant extracts, botanical extracts, sebum absorbents, sebum controlagents, vitamins, waxes, surfactants, detergents, emulsifiers,thickeners, propellant gases, skin protectants, film forming polymers,light scattering agents, and combinations thereof. In some of theseembodiments, the composition may be referred to as a skin carecomposition, a cosmetic composition, a sunscreen, a shower gel, a soap,a hydrogel, a cream, a lotion, a balm, foundation, lipstick, eyeliner, acuticle coat, a blush, etc., based on the particular personal careingredients utilized. Various species of such skin care ingredients areset forth below, with similar and alternative species known by one ofordinary skill in the art.

Examples of emollients include volatile or non-volatile silicone oils;silicone resins such as polypropylsilsesquioxane and phenyltrimethicone; silicone elastomers such as dimethicone crosspolymer;alkylmethylsiloxanes such as C₃₀₋₄₅ alkyl methicone; volatile ornon-volatile hydrocarbon compounds, such as squalene, paraffin oils,petrolatum oils and naphthalene oils; hydrogenated or partiallyhydrogenated polyisobutene; isoeicosane; squalane; isoparaffin;isododecane; isodecane or isohexa-decane; branched C₈-C₁₆ esters;isohexyl neopentanoate; ester oils such as isononyl isononanoate,cetostearyl octanoate, isopropyl myristate, palmitate derivatives (e.g.dextrin palmitate), stearates derivatives, diisostearyl malate,isostearyl isostearate and the heptanoates, octanoates, decanoates orricinoleates of alcohols or of polyalcohols, or mixtures thereof;hydrocarbon oils of plant origin, such as wheatgerm, sunflower,grapeseed, castor, shea, avocado, olive, soybean, sweet almond, palm,rapeseed, cotton seed, hazelnut, macadamia, jojoba, blackcurrant,evening primrose; or triglycerides of caprylic/capric acids; higherfatty acids, such as oleic acid, linoleic acid or linolenic acid, andmixtures thereof.

Examples of waxes include hydrocarbon waxes such as beeswax, lanolinwax, rice wax, carnauba wax, candelilla wax, microcrystalline waxes,paraffins, ozokerite, polyethylene waxes, synthetic wax, ceresin,lanolin, lanolin derivatives, cocoa butter, shellac wax, bran wax, capokwax, sugar cane wax, montan wax, whale wax, bayberry wax, silicone waxes(e.g. polymethylsiloxane alkyls, alkoxys and/or esters, C₃₀₋₄₅alkyldimethylsilyl polypropylsilsesquioxane), stearyl dimethicone,alkylmethylsiloxanes including long-chain alkyl groups inalkylmethylsiloxy units, and mixtures thereof.

Examples of moisturizers include lower molecular weight aliphatic diolssuch as propylene glycol and butylene glycol; polyols such as glycerineand sorbitol; and polyoxyethylene polymers such as polyethylene glycol200; hyaluronic acid and its derivatives, and mixtures thereof.

Examples of thickeners include acrylamide copolymers, acrylatecopolymers and salts thereof (such as sodium polyacrylate), xanthan gumand derivatives, cellulose gum and cellulose derivatives (such asmethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose,hydroxypropylcellulose, polypropylhydroxyethylcellulose), starch andstarch derivatives (such as hydroxyethylamylose and starch amylase),polyoxyethylene, carbomer, alginates (such as sodium alginate), arabicgum, cassia gum, carob gum, scleroglucan gum, gellan gum, rhamsan gum,karaya gum, carrageenan gum, guar gum and guar gum derivatives, cocamidederivatives (including cocamidopropyl betaine and cocamide MIPA), alkylalcohols (such as cetearyl alcohol, stearyl alcohol, and other fattyalcohols), gelatin, PEG-derivatives, saccharides (such as fructose,glucose) and saccharides derivatives (such as PEG-120 methyl glucosediolate), and mixtures thereof.

Examples of water phase stabilizing agents include electrolytes (e.g.alkali metal salts and alkaline earth salts, especially the chloride,borate, citrate, and sulfate salts of sodium, potassium, calcium andmagnesium, as well as aluminum chlorohydrate, and polyelectrolytes,especially hyaluronic acid and sodium hyaluronate), polyols (glycerine,propylene glycol, butylene glycol, and sorbitol), alcohols such as ethylalcohol, and hydrocolloids, and mixtures thereof.

Examples of pH controlling agents include any water soluble acid such asa carboxylic acid or a mineral acid such as hydrochloric acid, sulphuricacid, and phosphoric acid, monocarboxylic acid such as acetic acid andlactic acid, and polycarboxylic acids such as succinic acid, adipicacid, citric acid, and mixtures thereof.

Example of preservatives and cosmetic biocides include parabenderivatives (e.g. methylparaben, propylparaben), hydantoin derivatives,chlorhexidine and its derivatives, imidazolidinyl urea, diazolidinylurea, phenoxyethanol, silver derivatives, salicylate derivatives,triclosan, ciclopirox olamine, hexamidine, oxyquinoline and itsderivatives, PVP-iodine, zinc salts and derivatives such as zincpyrithione, methylchloroisothiazolinone, methylisothiazolinone, andmixtures thereof.

Examples of sebum absorbants or sebum control agents include silicasilylate, silica dimethyl silylate, dimethicone/vinyl dimethiconecrosspolymer, polymethyl methacrylate, cross-linked methylmethacrylate,aluminum starch octenylsuccinate, and mixtures thereof.

Examples of pigments and colorants include surface treated or untreatediron oxides, surface treated or untreated titanium dioxide, surfacetreated or untreated mica, silver oxide, silicates, chromium oxides,carotenoids, carbon black, ultramarines, chlorophyllin derivatives andyellow ocher. Examples of organic pigments include aromatic typesincluding azo, indigoid, triphenylmethane, anthraquinone, and xanthinedyes which are designated as D&C and FD&C blues, browns, greens,oranges, reds, yellows, etc, and mixtures thereof. Surface treatmentsinclude those treatments based on lecithin, silicone, silanes, fluorocompounds, and mixtures thereof.

Examples of silicone conditioning agents include silicone oils such asdimethicone; silicone gums such as dimethiconol; silicone resins such astrimethylsiloxy silicate, polypropyl silsesquioxane; siliconeelastomers; alkylmethylsiloxanes; organomodified silicone oils, such asamodimethicone, aminopropyl phenyl trimethicone, phenyl trimethicone,trimethyl pentaphenyl trisiloxane, silicone quaternium-16/glycidoxydimethicone crosspolymer, silicone quaternium-16; saccharide functionalsiloxanes; carbinol functional siloxanes; silicone polyethers; siloxanecopolymers (divinyldimethicone/dimethicone copolymer); acrylate oracrylic functional siloxanes; and mixtures or emulsions thereof.

Examples of cationic conditioning agents include guar derivatives suchas hydroxypropyltrimethylammonium derivative of guar gum; cationiccellulose derivatives, cationic starch derivatives; quaternary nitrogenderivatives of cellulose ethers; homopolymers of dimethyldiallylammonium chloride; copolymers of acrylamide and dimethyldiallyl ammoniumchloride; homopolymers or copolymers derived from acrylic acid ormethacrylic acid which contain cationic nitrogen functional groupsattached to the polymer by ester or amide linkages; polymeric quaternaryammonium salts of hydroxyethyl cellulose reacted with a fatty alkyldimethyl ammonium substituted epoxide; polycondensation products ofN,N′-bis-(2,3-epoxypropyl)-piperazine or piperazine-bis-acrylamide andpiperazine; and copolymers of vinylpyrrolidone and acrylic acid esterswith quaternary nitrogen functionality. Specific materials include thevarious polyquats, e.g. Polyquaternium-7, Polyquaternium-8,Polyquaternium-10, Polyquaternium-11, and Polyquaternium-23. Othercategories of conditioners include cationic surfactants such as cetyltrimethylammonium chloride, cetyl trimethylammonium bromide,stearyltrimethylammonium chloride, and mixtures thereof. In someinstances, the cationic conditioning agent is also hydrophobicallymodified, such as hydrophobically modified quaternizedhydroxyethylcellulose polymers; cationic hydrophobically modifiedgalactomannan ether; and mixtures thereof.

Examples of hydrophobic conditioning agents include guar derivatives;galactomannan gum derivatives; cellulose derivatives; and mixturesthereof.

UV absorbers and sunscreen agents include those which absorb ultravioletlight between about 290-320 nanometers (the UV-B region) and those whichabsorb ultraviolet light in the range of 320-400 nanometers (the UV-Aregion).

Some examples of sunscreen agents are aminobenzoic acid, cinoxate,diethanolamine methoxycinnamate, digalloyl trioleate, dioxybenzone,ethyl 4-[bis(Hydroxypropyl)]aminobenzoate, glyceryl aminobenzoate,homosalate, lawsone with dihydroxyacetone, menthyl anthranilate,octocrylene, ethylhexyl methoxycinnamate (or octyl methoxycinnamate),octyl salicylate (or ethylhexyl salicylate), oxybenzone, padimate O,phenylbenzimidazole sulfonic acid, red petrolatum, sulisobenzone,titanium dioxide, trolamine salicylate, and mixtures thereof.

Some examples of UV absorbers are acetaminosalol, allatoin PABA,benzalphthalide, benzophenone, benzophenone 1-12, 3-benzylidene camphor,benzylidenecamphor hydrolyzed collagen sulfonamide, benzylidene camphorsulfonic Acid, benzyl salicylate, bornelone, bumetriozole, butylmethoxydibenzoylmethane, butyl PABA, ceria/silica, ceria/silica talc,cinoxate, DEA-methoxycinnamate, dibenzoxazol naphthalene, di-t-butylhydroxybenzylidene camphor, digalloyl trioleate, diisopropyl methylcinnamate, dimethyl PABA ethyl cetearyldimonium tosylate, dioctylbutamido triazone, diphenyl carbomethoxy acetoxy naphthopyran, disodiumbisethylphenyl tiamminotriazine stilbenedisulfonate, disodiumdistyrylbiphenyl triaminotriazine stilbenedisulfonate, disodiumdistyrylbiphenyl disulfonate, drometrizole, drometrizole trisiloxane,ethyl dihydroxypropyl PABA, ethyl diisopropylcinnamate, ethylmethoxycinnamate, ethyl PABA, ethyl urocanate, etrocrylene ferulic acid,glyceryl octanoate dimethoxycinnamate, glyceryl PABA, glycol salicylate,homosalate, isoamyl p-methoxycinnamate, isopropylbenzyl salicylate,isopropyl dibenzolylmethane, isopropyl methoxycinnamate, octylmethoxycinnamate, menthyl anthranilate, menthyl salicylate,4-methylbenzylidene, camphor, octocrylene, octrizole, octyl dimethylPABA, ethyl hexyl methoxycinnamate, octyl salicylate, octyl triazone,PABA, PEG-25 PABA, pentyl dimethyl PABA, phenylbenzimidazole sulfonicacid, polyacrylamidomethyl benzylidene camphor, potassiummethoxycinnamate, potassium phenylbenzimidazole sulfonate, redpetrolatum, sodium phenylbenzimidazole sulfonate, sodium urocanate,TEA-phenylbenzimidazole sulfonate, TEA-salicylate, terephthalylidenedicamphor sulfonic acid, titanium dioxide, triPABA panthenol, urocanicacid, VA/crotonates/methacryloxybenzophenone-1 copolymer, and mixturesthereof.

Examples of skin protectants include allantoin, aluminium acetate,aluminium hydroxide, aluminium sulfate, calamine, cocoa butter, codliver oil, colloidal oatmeal, dimethicone, glycerin, kaolin, lanolin,mineral oil, petrolatum, shark liver oil, sodium bicarbonate, talc,witch hazel, zinc acetate, zinc carbonate, zinc oxide, and mixturesthereof.

Examples of dyes include 1-acetoxy-2-methylnaphthalene; acid dyes;5-amino-4-chloro-o-cresol; 5-amino-2,6-dimethoxy-3-hydroxypyridine;3-amino-2,6-dimethylphenol; 2-amino-5-ethylphenol HCl;5-amino-4-fluoro-2-methylphenol sulfate;2-amino-4-hydroxyethylaminoanisole; 2-amino-4-hydroxyethylaminoanisolesulfate; 2-amino-5-nitrophenol; 4-amino-2-nitrophenol;4-amino-3-nitrophenol; 2-amino-4-nitrophenol sulfate; m-aminophenol HCl;p-aminophenol HCl; m-aminophenol; o-aminophenol;4,6-bis(2-hydroxyethoxy)-m-phenylenediamine HCl;2,6-bis(2-hydroxyethoxy)-3,5-pyridinediamine HCl;2-chloro-6-ethylamino-4-nitrophenol; 2-chloro-5-nitro-N-hydroxyethylp-phenylenediamine; 2-chloro-p-phenylenediamine; 3,4-diaminobenzoicacid; 4,5-diamino-1-((4-chlorophenyl)methyl)-1H-pyrazole-sulfate;2,3-diaminodihydropyrazolo pyrazolone dimethosulfonate;2,6-diaminopyridine; 2,6-diamino-3-((pyridin-3-yl)azo)pyridine;dihydroxyindole; dihydroxyindoline; N,N-dimethyl-p-phenylenediamine;2,6-dimethyl-p-phenylenediamine; N,N-dimethyl-p-phenylenediaminesulfate; direct dyes; 4-ethoxy-m-phenylenediamine sulfate;3-ethylamino-p-cresol sulfate; N-ethyl-3-nitro PABA; gluconamidopropylaminopropyl dimethicone; Haematoxylon brasiletto wood extract; HC dyes;Lawsonia inermis (Henna) extract; hydroxyethyl-3,4-methylenedioxyanilineHCl; hydroxyethyl-2-nitro-p-toluidine; hydroxyethyl-p-phenylenediaminesulfate; 2-hydroxyethyl picramic acid; hydroxypyridinone;hydroxysuccinimidyl C₂₁-C₂₂ isoalkyl acidate; isatin; Isatis tinctorialeaf powder; 2-methoxymethyl-p-phenylenediamine sulfate;2-methoxy-p-phenylenediamine sulfate; 6-methoxy-2,3-pyridinediamine HCl;4-methylbenzyl 4,5-diamino pyrazole sulfate; 2,2′-methylenebis4-aminophenol; 2,2′-methylenebis-4-aminophenol HCl;3,4-methylenedioxyaniline; 2-methylresorcinol; methylrosaniliniumchloride; 1,5-naphthalenediol; 1,7-naphthalenediol; 3-nitro-p-Cresol;2-nitro-5-glyceryl methylaniline; 4-nitroguaiacol;3-nitro-p-hydroxyethylaminophenol; 2-nitro-N-hydroxyethyl-p-anisidine;nitrophenol; 4-nitrophenyl aminoethylurea; 4-nitro-o-phenylenediaminedihydrochloride; 2-nitro-p-phenylenediamine dihydrochloride;4-nitro-o-phenylenediamine HCl; 4-nitro-m-phenylenediamine;4-nitro-o-phenylenediamine; 2-nitro-p-phenylenediamine;4-nitro-m-phenylenediamine sulfate; 4-nitro-o-phenylenediamine sulfate;2-nitro-p-phenylenediamine sulfate; 6-nitro-2,5-pyridinediamine;6-nitro-o-toluidine; PEG-3 2,2′-di-p-phenylenediamine;p-phenylenediamine HCl; p-phenylenediamine sulfate; phenyl methylpyrazolone; N-phenyl-p-phenylenediamine HCl; pigment blue 15:1; pigmentviolet 23; pigment yellow 13; pyrocatechol; pyrogallol; resorcinol;sodium picramate; sodium sulfanilate; solvent yellow 85; solvent yellow172; tetraaminopyrimidine sulfate; tetrabromophenol blue;2,5,6-triamino-4-pyrimidinol sulfate; 1,2,4-trihydroxybenzene.

Examples of fragrances include perfume ketones and perfume aldehydes.Illustrative of the perfume ketones are buccoxime; iso jasmone; methylbeta naphthyl ketone; musk indanone; tonalid/musk plus; Alpha-Damascone,Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose,Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone,Alpha-Ionone, Beta-Ionone, Gamma-Methyl so-called Ionone, Fleuramone,Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl-Cedrenyl-ketone orMethyl-Cedrylone, Acetophenone, Methyl-Acetophenone,Para-Methoxy-Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-Acetone,Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery Ketone or Livescone,6-Isopropyldecahydro-2-naphtone, Dimethyl-Octenone, Freskomenthe,4-(1-Ethoxyvinyl)-3,3,5,5,-tetramethyl-Cyclohexanone, Methyl-Heptenone,2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)-cyclopentanone,1-(p-Menthen-6(2)-yl)-1-propanone,4-(4-Hydroxy-3-methoxyphenyl)-2-butanone,2-Acetyl-3,3-Dimethyl-Norbornane,6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-Damascol, Dulcinylor Cassione, Gelsone, Hexylon, Isocyclemone E, Methyl Cyclocitrone,Methyl-Lavender-Ketone, Orivon, Para-tertiary-Butyl-Cyclohexanone,Verdone, Delphone, Muscone, Neobutenone, Plicatone, Veloutone,2,4,4,7-Tetramethyl-oct-6-en-3-one, and Tetrameran. The fragrance may bederived or extracted from flowers, seeds, leaves, and/or roots ofplants, seaweed, etc. The fragrance may be extracted from an animal,e.g. from a secretion gland, and may be a musk or sperm oil. Thefragrance may also be artificially synthesized, e.g. menthol, acetate,vanilla, etc.

In specific embodiments, the perfume ketones are selected for odorcharacter from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone,Gamma-Methyl-Ionone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one,Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate,methyl cedrylone, and mixtures thereof.

In specific embodiments, the perfume aldehyde is selected for odorcharacter from adoxal; anisic aldehyde; cymal; ethyl vanillin;florhydral; helional; heliotropin; hydroxycitronellal; koavone; lauricaldehyde; lyral; methyl nonyl acetaldehyde; P. T. bucinal; phenylacetaldehyde; undecylenic aldehyde; vanillin;2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amyl cinnamicaldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3-(4-tertbutylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyl propanal,2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl) butanal,3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6-octadien-1-al,3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy]acetaldehyde,4-isopropylbenzyaldehyde,1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde,2,4-dimethyl-3-cyclohexen-1-carboxaldehyde,2-methyl-3-(isopropylphenyl)propanal, 1-decanal; decyl aldehyde,2,6-dimethyl-5-heptenal,4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal,octahydro-4,7-methano-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethyl hydrocinnamaldehyde,alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde,3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde,m-cymene-7-carboxaldehyde, alpha-methyl phenyl acetaldehyde,7-hydroxy-3,7-dimethyl octanal, Undecenal,2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde,4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaldehyde, 1-dodecanal,2,4-dimethyl cyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al,2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal,2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal,dihydrocinnamic aldehyde,1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbox aldehyde, 5 or 6methoxy 10 hexahydro-4,7-methanoindan-1 or 2-carboxaldehyde,3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al,4-hydroxy-3-methoxy benzaldehyde,1-methyl-3-(4-methylpentyl)-3-cyclhexenecarboxaldehyde,7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal,paratolylacetaldehyde; 4-methylphenylacetaldehyde,2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butena I,ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde,5,9-dimethyl-4,8-decadienal, peony aldehyde(6,10-dimethyl-3-oxa-5,9-undecadien-1-al),hexahydro-4,7-methanoindan-1-carboxaldehyde, 2-methyl octanal,alpha-methyl-4-(1-methyl ethyl)benzene acetaldehyde,6,6-dimethyl-2-norpinene-2-propionaldehyde, para methyl phenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethyl hexanal,Hexahydro-8,8-dimethyl-2-naphthaldehyde,3-propyl-bicyclo[2.2.1]-hept-5-ene-2-carbaldehyde, 9-decenal,3-methyl-5-phenyl-1-pentanal, methylnonyl acetaldehyde, hexanal,trans-2-hexenal, 1-p-menthene-q-carboxaldehyde and mixtures thereof.

Examples of antioxidants are acetyl cysteine, arbutin, ascorbic acid,ascorbic acid polypeptide, ascorbyl dipalmitate, ascorbyl methylsilanolpectinate, ascorbyl palmitate, ascorbyl stearate, BHA, p-hydroxyanisole,BHT, t-butyl hydroquinone, caffeic acid, Camellia sinensis oil, chitosanascorbate, chitosan glycolate, chitosan salicylate, chlorogenic acids,cysteine, cysteine HCl, decyl mercaptomethylimidazole, erythorbic acid,diamylhydroquinone, di-t-butylhydroquinone, dicetyl thiodipropionate,dicyclopentadiene/t-butylcresol copolymer, digalloyl trioleate, dilaurylthiodipropionate, dimyristyl thiodipropionate, dioleyl tocopherylmethylsilanol, isoquercitrin, diosmine, disodium ascorbyl sulfate,disodium rutinyl disulfate, distearyl thiodipropionate, ditridecylthiodipropionate, dodecyl gallate, ethyl ferulate, ferulic acid,hydroquinone, hydroxylamine HCl, hydroxylamine sulfate, isooctylthioglycolate, kojic acid, madecassicoside, magnesium ascorbate,magnesium ascorbyl phosphate, melatonin, methoxy-PEG-7 rutinylsuccinate, methylene di-t-butylcresol, methylsilanol ascorbate,nordihydroguaiaretic acid, octyl gallate, phenylthioglycolic acid,phloroglucinol, potassium ascorbyl tocopheryl phosphate,thiodiglycolamide, potassium sulfite, propyl gallate, rosmarinic acid,rutin, sodium ascorbate, sodium ascorbyl/cholesteryl phosphate, sodiumbisulfite, sodium erythorbate, sodium metabisulfide, sodium sulfite,sodium thioglycolate, sorbityl furfural, tea tree (Melaleucaaftemifolia) oil, tocopheryl acetate, tetrahexyldecyl ascorbate,tetrahydrodiferuloylmethane, tocopheryl linoleate/oleate, thiodiglycol,tocopheryl succinate, thiodiglycolic acid, thioglycolic acid, thiolacticacid, thiosalicylic acid, thiotaurine, retinol, tocophereth-5,tocophereth-10, tocophereth-12, tocophereth-18, tocophereth-50,tocopherol, tocophersolan, tocopheryl linoleate, tocopheryl nicotinate,tocoquinone, o-tolyl biguanide, tris(nonylphenyl) phosphite, ubiquinone,zinc dibutyldithiocarbamate, and mixtures thereof.

Examples of propellant gases include carbon dioxide, nitrogen, nitrousoxide, volatile hydrocarbons such as butane, isobutane, or propane, andchlorinated or fluorinated hydrocarbons such as dichlorodifluoromethaneand dichlorotetrafluoroethane or dimethylether; and mixtures thereof.

In a specific embodiment, the composition is a sunscreen. In theseembodiments, personal care ingredient comprises the sunscreen agent. Thesunscreen agent may be, for example, a sunscreen additive, an SPFbooster, a photostabilizer, a film-forming polymer, etc. The sunscreenmay be also or alternatively be utilized in sunless tanningapplications. Specific examples of sunscreen agents are set forth above.

In other embodiments, the personal care ingredient comprises a hair careingredient. In these embodiments, the composition may be referred to asa hair care composition. If utilized to prepare the composition, thehair care ingredient is typically selected from conditioning agents(which may be silicone, cationic, hydrophobic, etc.), colorants, dyes,ultraviolet (UV) absorbers, preservatives, plant extracts, fattyalcohols, vitamins, fragrance, anti-dandruff agents, color careadditives, pearlising agents, pH controlling agents, electrolytes,chelating agents, styling agents, ceramides, amino-acid derivatives,suspending agents, surfactants, detergents, emulsifiers, thickeners,oxidizing agents, reducing agents, film-forming polymers, andcombinations thereof. With some of these hair care embodiments, thecomposition may be referred to as a shampoo, a rinse-off conditioner, aleave-in conditioner, a gel, a pomade, a serum, a spray, a coloringproduct, or mascara. Examples of many of these hair care ingredients areset forth above as suitable personal care ingredients.

Examples of oxidizing agents are ammonium persulfate, calcium peroxide,hydrogen peroxide, magnesium peroxide, melamine peroxide, potassiumbromate, potassium caroate, potassium chlorate, potassium persulfate,sodium bromate, sodium carbonate peroxide, sodium chlorate, sodiumiodate, sodium perborate, sodium persulfate, strontium dioxide,strontium peroxide, urea peroxide, zinc peroxide, and mixtures thereof.

Examples of reducing agents are ammonium bisufite, ammonium sulfite,ammonium thioglycolate, ammonium thiolactate, cystemaine HCl, cystein,cysteine HCl, ethanolamine thioglycolate, glutathione, glycerylthioglycolate, glyceryl thioproprionate, hydroquinone, p-hydroxyanisole,isooctyl thioglycolate, magnesium thioglycolate, mercaptopropionic acid,potassium metabisulfite, potassium sulfite, potassium thioglycolate,sodium bisulfite, sodium hydrosulfite, sodium hydroxymethane sulfonate,sodium metabisulfite, sodium sulfite, sodium thioglycolate, strontiumthioglycolate, superoxide dismutase, thioglycerin, thioglycolic acid,thiolactic acid, thiosalicylic acid, zinc formaldehyde sulfoxylate, andmixtures thereof.

Examples of antidandruff agents include pyridinethione salts, seleniumcompounds such as selenium disulfide, and soluble antidandruff agents,and mixtures thereof.

In other embodiments, the personal care ingredient comprises a nail careingredient. In these embodiments, the composition may be referred to asa nail care composition. If utilized to prepare the composition, thenail care ingredient may be any ingredient utilized in nail carecompositions, e.g. nail polishes, nail gels, nail tips, acrylicfinishes, etc. Examples of such nail care ingredients include pigments,resins, solvents, volatile halogenated compounds (e.g.methoxynonafluorobutane and/or ethoxynonafluorobutane), etc.

More specifically, examples of nail care ingredients include butylacetate; ethyl acetate; nitrocellulose; acetyl tributyl citrate;isopropyl alcohol; adipic acid/neopentyl glycol/trimelitic anhydridecopolymer; stearalkonium bentonite; acrylates copolymer; calciumpantothenate; Cetraria islandica extract; Chondrus crispus;styrene/acrylates copolymer; trimethylpentanediyl dibenzoate-1;polyvinyl butyral; N-butyl alcohol; propylene glycol; butylene glycol;mica; silica; tin oxide; calcium borosilicate; syntheticfluorphlogopite; polyethylene terephtalate; sorbitan lauratederivatives; talc; jojoba extract; diamond powder; isobutylphenoxy epoxyresin; silk powder; and mixtures thereof.

In other embodiments, the personal care ingredient comprises a toothcare ingredient. In these embodiments, the composition may be referredto as a tooth care composition. One specific example of such a toothcare composition is toothpaste. Another example of a tooth carecomposition is a tooth whitening composition. The tooth care ingredientmay be any tooth care ingredient suitable for the tooth carecomposition, such as an abrasive compound (e.g. aluminum hydroxide,calcium carbonate, silica, zeolite), a fluoride compound, a surfactant,a flavorant, a remineralizer, an antibacterial agent, etc.

In certain embodiments, the personal care ingredient comprises afilm-forming polymer, which may be utilized as the personal careingredient whether the composition is utilized for skin care, hair care,etc. “Film-forming polymer,” as used herein, means a polymer or oligomerwhich is capable of, by itself or optionally in the presence of afilm-forming agent, forming a film on a substrate. The film-formingpolymer may form the film upon an application of a curing condition,e.g. the application of heat, exposure to atmospheric conditions, etc.Alternatively, the film-forming polymer may form the film uponevaporation of any carrier vehicle in which the film-forming polymer mayoptionally be disposed. The film-forming polymer may undergo a reaction,e.g. the film-forming polymer may become cross-linked or otherwiseinclude additional bonds, when forming the film. However, thefilm-forming polymer may form the film in the absence of such areaction. The film-forming polymer may be a gelling agent. Thefilm-forming polymer is particularly advantageous when the compositionis the sunscreen, although the personal care ingredient may comprise thefilm-forming polymer in other compositions as well.

The substrate on which the film is formed may be any substrate, althoughthe substrate is generally a portion of a mammal, particularly a human,as described in greater detail below with reference to the treatmentmethod. Specific examples of suitable substrates include skin, hair, andnails.

Generally, the film is continuous, although the film may have a varyingthickness. By continuous, it is meant that the film does not define anyapertures. The film may be referred to as being macroscopicallycontinuous. The film may be supported by the substrate, or may bebonded, e.g. physically and/or chemically, to the substrate. In certainembodiments, the film is optionally removable from the substrate, e.g.the film may be peelable from the substrate. The film may remain intactas a free-standing film upon being separated from the substrate or maybe separated through application of shear, which may damage and/ordestroy continuity of the film.

Specific examples of film-forming polymers that are suitable includeacrylic polymers, silicone resins (e.g. polypropylsilsesquioxane),polyurethanes, polyurethane-acrylics, polyesters,polyester-polyurethanes, polyether-polyurethanes, polyesteramides,alkyds, polyamides, polyureas, polyurea-polyurethanes, cellulose-basedpolymers (e.g. nitrocellulose), silicones, acrylic-silicones,polyacrylamides, fluoropolymers, polyisoprenes, and any copolymers orterpolymers thereof or including one of these. The term “silicones,” asused herein with reference to suitable film-forming polymers, includeslinear, branched, and resinous silicones, although resinous siliconesare generally referred to as silicone resins rather than polymers. Thesilicone may be modified, e.g. the silicone may be a silicone-graftedacrylic polymer.

As introduced above, the film-forming polymer may be disposed in acarrier vehicle, which may partially or fully solubilize thefilm-forming polymer. Depending on a selection of the film-formingpolymer, the carrier vehicle may be, for example, an oil, e.g. anorganic oil and/or a silicone oil, a solvent, water, etc. Thefilm-forming polymer may be in the form of polymer particles, which areoptionally surface-stabilized with at least one stabilizer, and thepolymer particles may be present as a dispersion or emulsion.

The film-forming polymer may be a block polymer, which may bestyrene-free. Typically, the block polymer comprises at least one firstblock and at least one second block, which may be linked together via anintermediate block comprising at least one constituent monomer of thefirst block and at least one constituent monomer of the second block.Generally, the glass transition temperatures of the first and secondblocks are different from one another.

Monomers that may be utilized to prepare the block polymer include, forexample, methyl methacrylate, isobutyl (meth)acrylate and isobornyl(meth)acrylate, methyl acrylate, isobutyl acrylate, n-butylmethacrylate, cyclodecyl acrylate, neopentyl acrylate,isodecylacrylamide 2-ethylhexyl acrylate and mixtures thereof.

In specific embodiments, the film-forming polymer be obtained orgenerated via free-radical polymerization. For example, the film-formingpolymer may be generated via free-radical polymerization of at least oneacrylic monomer and at least one silicone- or hydrocarbon-basedmacromonomer including a polymerizable end group.

Specific examples of hydrocarbon-based macromonomers includehomopolymers and copolymers of linear or branched C₈-C₂₂ alkyl acrylateor methacrylate. The polymerizable end group may be a vinyl group or a(meth)acrylate group, e.g. poly(2-ethylhexyl acrylate) macromonomers;poly(dodecyl acrylate) or poly(dodecyl methacrylate) macromonomers;poly(stearyl acrylate) or poly(stearyl methacrylate) macromonomers, etc.Such macromonomers generally include one (meth)acrylate group as thepolymerizable end group.

Additional examples of hydrocarbon-based macromonomers includepolyolefins containing an ethylenically unsaturated end group (as thepolymerizable end group), e.g. a (meth)acrylate end group. Specificexamples of such polyolefins include polyethylene macromonomers,polypropylene macromonomers, polyethylene/polypropylene copolymermacromonomers, polyethylene/polybutylene copolymer macromonomers,polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprenemacromonomers; polybutadiene macromonomers; and poly(ethylene/butylene)-polyisoprene macromonomers.

Examples of silicone-based macromonomers include organopolysiloxanescontaining the polymerizable end group, e.g. a (meth)acrylate end group.The organopolysiloxane may be linear, branched, partially branched, orresinous. In various embodiments, the organopolysiloxane is linear. Inthese embodiments, the organopolysiloxane may be polydimethylsiloxane,although hydrocarbon groups other than methyl groups may be presenttherein along with or in lieu of methyl groups. Typically, thepolymerizable end group is terminal, although the polymerizable endgroup may optionally be pendant. One specific example of asilicone-based macromonomer is a monomethacryloxypropylpolydimethylsiloxane.

In certain embodiments, the film-forming polymer is an organicfilm-forming polymer that is soluble in oil as the carrier vehicle. Inthese embodiments, the film-forming polymer may be referred to as aliposoluble polymer. The liposoluble polymer may be of any type andspecific examples thereof include those comprising or formed fromolefins, cycloolefins, butadiene, isoprene, styrene, vinyl ethers, vinylesters, vinyl amides, (meth)acrylic acid esters or amides, etc.

In one embodiment, the liposoluble polymer is formed from monomersselected from the group consisting of isooctyl (meth)acrylate, isononyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate,isopentyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl(meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate,tridecyl (meth)acrylate, stearyl (meth)acrylate, and combinationsthereof.

Alternatively still, the liposoluble polymer may be an acrylic-siliconegrafted polymer, which typically includes a silicone backbone andacrylic grafts or alternatively includes an acrylic backbone andsilicone grafts.

The film-forming polymer may be halogenated, e.g. the film-formingpolymer may include fluorine atoms.

Alternatively as introduced above, the film-forming polymer may be acellulose-based polymer, such as nitrocellulose, cellulose acetate,cellulose acetobutyrate, cellulose acetopropionate or ethylcellulose.Alternatively still, the film-forming polymer may comprise apolyurethane, an acrylic polymer, a vinyl polymer, a polyvinyl butyral,an alkyd resin, or resins derived from aldehyde condensation products,such as arylsulfonamide-formaldehyde resins.

Further, as introduced above, the film-forming polymer may comprise thesilicone, which may be linear, branched, or resinous. Resinous siliconesgenerally include at least one T and/or Q unit, as understood in theart. Examples of resinous silicones include silsesquioxanes. Thesilicone may include any combination of M, D, T, and Q units so long asthe silicone constitutes the film-forming polymer.

When the film-forming polymer comprises the silicone, the film-formingpolymer may comprise an amphiphilic silicone. Amphiphilic siliconestypically contain a silicone portion which is compatible with a siliconemedium, and a hydrophilic portion. The hydrophilic portion may be, forexample, the residue of a compound selected from alcohols and polyols,having 1 to 12 hydroxyl groups, and polyoxyalkylenes (e.g. thosecontaining oxypropylene units and/or oxyethylene units).

The amphiphilic silicone may be an oil with or without gelling activity.Oils of this kind may comprise, for example, dimethicone copolyols,bis-hydroxyethoxypropyl dimethicone, etc.

In one embodiment, the film-forming polymer comprises a silicone organicelastomer gel. Silicone organic elastomer gels comprise linearorganopolysiloxane chains crosslinked via polyoxyalkylenes. The siliconeorganic elastomer gel may further include hydrophilic polyetherfunctionality pending from the linear organopolysiloxane chains.Specific examples of suitable silicone organic elastomer gels aredisclosed in International (PCT) Appln. No. PCT/US2010/020110.

In various embodiments, the personal care ingredient may comprise or bereferred to as a personal care active, a health care active, orcombination thereof (collectively “active” or “actives”). As usedherein, a “personal care active” means any compound or mixtures ofcompounds that are known in the art as additives in personal careformulations, typically for providing a cosmetic and/or aestheticbenefit. A “healthcare active” means any compound or mixtures ofcompounds that are known in the art to provide a pharmaceutical ormedical benefit. Thus, “healthcare active” includes materials consideredas an active ingredient or active drug ingredient as generally used anddefined by the United States Department of Health & Human Services Foodand Drug Administration, contained in Title 21, Chapter I, of the Codeof Federal Regulations, Parts 200-299 and Parts 300-499. Specificpersonal care actives and health care actives are described below. Thesepersonal care actives and health care actives may constitute thepersonal care ingredient whether the personal care ingredient isutilized to form, for example, the AP/DEO composition, the skin carecomposition, the hair care composition, the nail care composition,and/or the tooth care composition. For example, in various embodiments,the same personal care ingredient may be utilized to form either thehair care composition or the skin care composition. As understood in theart, at least some of the personal care actives described below arespecies of certain personal care ingredients introduced above withrespect to the skin care composition, the hair care composition, thenail care composition, and the tooth care composition, respectively. Forexample, numerous species of plant or vegetable extracts are describedbelow, which are exemplary examples of plant extracts set forth above assuitable personal care ingredients. The active ingredients or activesdescribed below may constitute the personal care ingredient of thecomposition or may be utilized in combination therewith.

Useful active ingredients for use in the composition include vitaminsand vitamin derivatives, including “pro-vitamins”. Vitamins usefulherein include, but are not limited to, Vitamin A1, retinol, C₂-C₁₈esters of retinol, vitamin E, tocopherol, esters of vitamin E, andmixtures thereof. Retinol includes trans-retinol, 1, 3-cis-retinol,11-cis-retinol, 9-cis-retinol, and 3,4-didehydro-retinol, Vitamin C andits derivatives, Vitamin B1, Vitamin B2, Pro Vitamin B5, panthenol,Vitamin B6, Vitamin B112, niacin, folic acid, biotin, and pantothenicacid. Other suitable vitamins and the INCI names for the vitaminsconsidered included herein are ascorbyl dipalmitate, ascorbylmethylsilanol pectinate, ascorbyl palmitate, ascorbyl stearate, ascorbylglucocide, sodium ascorbyl phosphate, sodium ascorbate, disodiumascorbyl sulfate, potassium (ascorbyl/tocopheryl) phosphate. In general,retinol, all trans retinoic acid and derivatives, isomers and analogsthereof, are collectively termed “retinoids”.

RETINOL, it should be noted, is an International Nomenclature CosmeticIngredient Name (INCI) designated by The Cosmetic, Toiletry, andFragrance Association (CTFA), Washington D.C., for vitamin A. Othersuitable vitamins and the INCI names for the vitamins consideredincluded herein are RETINYL ACETATE, RETINYL PALMITATE, RETINYLPROPIONATE, α-TOCOPHEROL, TOCOPHERSOLAN, TOCOPHERYL ACETATE, TOCOPHERYLLINOLEATE, TOCOPHERYL NICOTINATE, and TOCOPHERYL SUCCINATE.

Some examples of commercially available products suitable for use hereinare Vitamin A Acetate and Vitamin C, both products of Fluka Chemie AG,Buchs, Switzerland; COVI-OX T-50, a vitamin E product of HenkelCorporation, La Grange, Illinois; COVI-OX T-70, another vitamin Eproduct of Henkel Corporation, La Grange, Illinois; and vitamin EAcetate, a product of Roche Vitamins & Fine Chemicals, Nutley, N.J.

The active can be a protein, such as an enzyme. Enzymes include, but arenot limited to, commercially available types, improved types,recombinant types, wild types, variants not found in nature, andmixtures thereof. For example, suitable enzymes include hydrolases,cutinases, oxidases, transferases, reductases, hemicellulases,esterases, isomerases, pectinases, lactases, peroxidases, laccases,catalases, and mixtures thereof. Hydrolases include, but are not limitedto, proteases (bacterial, fungal, acid, neutral or alkaline), amylases(alpha or beta), lipases, mannanases, cellulases, collagenases,lisozymes, superoxide dismutase, catalase, and mixtures thereof.Protease include, but are not limited to, trypsin, chymotrypsin, pepsin,pancreatin and other mammalian enzymes; papain, bromelain and otherbotanical enzymes; subtilisin, epidermin, nisin,naringinase(L-rhammnosidase) urokinase and other bacterial enzymes.Lipase include, but are not limited to, triacyl-glycerol lipases,monoacyl-glycerol lipases, lipoprotein lipases, e.g. steapsin, erepsin,pepsin, other mammalian, botanical, bacterial lipases and purified ones.In a specific embodiment, natural papain is utilized as the enzyme.Further, stimulating hormones, e.g. insulin, can be used together withthe enzyme(s) to boost effectiveness.

The active may also be one or more plant or vegetable extract. Examplesof these components are as follows: Ashitaba extract, avocado extract,hydrangea extract, Althea extract, Arnica extract, aloe extract, apricotextract, apricot kernel extract, Ginkgo Biloba extract, fennel extract,turmeric[Curcuma] extract, oolong tea extract, rose fruit extract,Echinacea extract, Scutellaria root extract, Phellodendro bark extract,Japanese Coptis extract, Barley extract, Hyperium extract, White Nettleextract, Watercress extract, Orange extract, Dehydrated saltwater,seaweed extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzedsilk, Chamomile extract, Carrot extract, Artemisia extract, Glycyrrhizaextract, hibiscustea extract, Pyracantha Fortuneana Fruit extract, Kiwiextract, Cinchona extract, cucumber extract, guanocine, Gardeniaextract, Sasa Albo-marginata extract, Sophora root extract, Walnutextract, Grapefruit extract, Clematis extract, Chlorella extract,mulberry extract, Gentiana extract, black tea extract, yeast extract,burdock extract, rice bran ferment extract, rice germ oil, comfreyextract, collagen, cowberry extract, Gardenia extract, Asiasarum Rootextract, Family of Bupleurum extract, Salvia extract, Saponaria extract,Bamboo extract, Crataegus fruit extract, Zanthoxylum fruit extract,shiitake extract, Rehmannia root extract, gromwell extract, Perillaextract, linden extract, Filipendula extract, peony extract, CalamusRoot extract, white birch extract, Horsetail extract, Hedera Helix(Ivy)extract, hawthorn extract, Sambucus nigra extract, Achillea millefoliumextract, Mentha piperita extract, sage extract, mallow extract, Cnidiumofficinale Root extract, Japanese green gentian extract, soybeanextract, jujube extract, thyme extract, tea extract, clove extract,Gramineae imperata cyrillo extract, Citrus unshiu peel extract JapaneseAngellica Root extract, Calendula extract, Peach Kernel extract, Bitterorange peel extract, Houttuyna cordata extract, tomato extract, nattoextract, Ginseng extract, Green tea extract (camelliea sinesis), garlicextract, wild rose extract, hibiscus extract, Ophiopogon tuber extract,Nelumbo nucifera extract, parsley extract, honey, Hamamelis extract,Parietaria extract, Isodonis herba extract, bisabolol extract, Loquatextract, coltsfoot extract, butterbur extract, Porid cocos wolf extract,extract of butcher's broom, grape extract, propolis extract, luffaextract, safflower extract, peppermint extract, linden tree extract,Paeonia extract, hop extract, pine tree extract, horse chestnut extract,Mizu-bashou [Lysichiton camtschatcese] extract, Mukurossi peel extract,Melissa extract, peach extract, cornflower extract, Eucalyptus extract,saxifrage extract, citron extract, Coix extract, mugwort extract,lavender extract, apple extract, lettuce extract, lemon extract, Chinesemilk vetch extract, rose extract, rosemary extract, Roman Chamomileextract, royal jelly extract, and combinations thereof.

Representative, non-limiting examples of healthcare actives useful asdrugs in the present compositions are described below. One or more ofthe drugs can be used, either alone or in combination with the activesand/or personal care ingredients described above.

The composition may include an antiparasite agent. The antiparasiteagent can be of any type. Examples of antiparasite agents include, butare not limited to, hexachlorobenzene, carbamate, naturally occurringpyrethroids, permethrin, allethrin, malathion, piperonyl butoxide, andcombinations thereof.

The composition may include an antimicrobial agent, also referred to asgermicidal agent. The antimicrobial agent can be of any type. Examplesof antimicrobial agents include, but are not limited to, phenols,including cresols and resorcinols. Such compositions may be used totreat infections of the skin. An example of a very common skin infectionis acne, which involve infestation of the sebaceous gland with P. acnes,as well as Staphylococus aurus or Pseudomonas. Examples of usefulantiacne actives include the keratolytics such as salicylic acid(o-hydroxybenzoic acid), derivatives of salicylic acid such as5-octanoyl salicylic acid, and resorcinol; retinoids such as retinoicacid and its derivatives (e.g. cis and trans); sulfur-containing D and Lamino acids and their derivatives and salts, particularly their N-acetylderivatives, e.g. N-acetyl-L-cysteine; lipoic acid; antibiotics andantimicrobials such as benzoyl peroxide, octopirox, tetracycline,2,4,4′-trichloro-2′-hydroxy diphenyl ether, 3,4,4′-trichlorobanilide,azelaic acid and its derivatives, phenoxyethanol, phenoxypropanol,phenoxyisopropanol, ethyl acetate, clindamycin and meclocycline;sebostats such as flavonoids; and bile salts such as scymnol sulfate andits derivatives, deoxycholate and cholate; parachlorometaxylenol; andcombinations thereof.

Phenols, in concentrations of about 0.2, 1.0, and 1.3, % by weight, aregenerally bacteriostatic, bactericidal, and fungicidal, respectively.Several phenol derivatives are more potent than phenol itself, and themost important among these are the halogenated phenols and bis-phenols,the alkyl-substituted phenols and the resorcinols. Hydrophobicantibacterials include triclosan, triclocarbon, eucalyptol, menthol,methylsalicylate, thymol, and combinations thereof.

The composition may include an antifungal agent. The antifungal agentcan be of any type. Examples of antifungal agents include, but are notlimited to, azoles, diazoles, triazoles, miconazole, fluconazole,ketoconazole, clotrimazole, itraconazole griseofulvin, ciclopirox,amorolfine, terbinafine, Amphotericin B, potassium iodide, flucytosine(5FC) and combinations thereof. U.S. Pat. No. 4,352,808 discloses3-aralkyloxy-2, 3-dihydro-2-(1H-imidazolylmethyl)benzo[b]thiophenecompounds having antifungal and antibacterial activity, which areincorporated herein by reference.

The composition may include a steroidal anti-inflammatory agent. Thesteroidal anti-inflammatory agent can be of any type. Examples ofsteroidal anti-inflammatory agents include, but are not limited to,corticosteroids such as hydrocortisone, hydroxyltriamcinolonealphamethyl dexamethasone, dexamethasone-phosphate, beclomethasonedipropionate, clobetasol valerate, desonide, desoxymethasone,desoxycorticosterone acetate, dexamethasone, dichlorisone, diflorasonediacetate, diflucortolone valerate, fluadrenolone, fluclaroloneacetonide, fludrocortisone, flumethasone pivalate, fluosinoloneacetonide, fluocinonide, flucortine butylester, fluocortolone,fluprednidene (fluprednylidene)acetate, flurandrenolone, halcinonide,hydrocortisone acetate, hydrocortisone butyrate, methylprednisolone,triamcinolone acetonide, cortisone, cortodoxone, flucetonide,fludrocortisone, difluorosone diacetate, fluradrenalone acetonide,medrysone, amc, amcinafide, betamethasone and the balance of its esters,chlorprednisone, chlorprednisone acetate, clocortelone, clescinolone,dichlorisone, difluprednate, flucloronide, flunisolide, fluoromethalone,fluperolone, fluprednisolone, hydrocortisone valerate, hydrocortisonecyclopentylproprionate, hydrocortamate, meprednisone, paramethasone,prednisolone, prednisone, beclomethasone dipropionate, betamethasonedipropionate, triamcinolone, and combinations thereof.

Topical antihistaminic preparations currently available include 1percent and 2 percent diphenhydramine (Benadryl® and Caladryl®), 5percent doxepin (Zonalon®) cream, phrilamine maleate, chlorpheniramineand tripelennamine, phenothiazines, promethazine hydrochloride(Phenergan®) and dimethindene maleate. These drugs, as well asadditional antihistamines can also be included in the composition.Additionally, so-called “natural” anti-inflammatory agents may beuseful. For example, candelilla wax, alpha bisabolol, aloe vera,Manjistha (extracted from plants in the genus Rubia, particularly Rubiacordifolia), and Guggal (extracted from plants in the genus Commiphora,particularly Commiphora mukul, may be used as an active in thecomposition.

The composition may include a non-steroidal anti-inflammatory drug(NSAID). The NSAID can be of any type. Examples of NSAIDs include, butare not limited to, the following NSAID categories: propionic to acidderivatives; acetic acid derivatives; fenamic acid derivatives;biphenylcarboxylic acid derivatives; and oxicams. Such NSAIDs aredescribed in the U.S. Pat. No. 4,985,459, which is incorporated hereinby reference. Further examples include, but are not limited to, acetylsalicylic acid, ibuprofen, naproxen, benoxaprofen, flurbiprofen,fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen,oxaprozin, pranoprofen, mniroprofen, tioxaprofen, suprofen,alminoprofen, tiaprofenic acid, fluprofen, bucloxic acid, andcombinations thereof.

The composition may include an antioxidant/radical scavenger. Theantioxidant can be of any type. Examples of antioxidants include, butare not limited to, ascorbic acid (vitamin C) and its salts, tocopherol(vitamin E), and its derivatives such as tocopherol sorbate, otheresters of tocopherol, butylated hydroxy benzoic acids and their salts,6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (commerciallyavailable under the trade name Trolox®), gallic acid and its alkylesters, especially propyl gallate, uric acid and its salts and alkylesters, sorbic acid and its salts, the ascorbyl esters of fatty acids,amines (e.g. N,N-diethylhydroxylamine, amino-guanidine), sulfhydrylcompounds (e.g. glutathione), and dihydroxy fumaric acid and its saltsmay be used, as well as EDTA, BHT and the like, and combinationsthereof.

The composition may include an antibiotic. The antibiotic can be of anytype. Examples of antibiotics include, but are not limited to,chloramphenicol, tetracyclines, synthetic and semi-synthesicpenicillins, beta-lactames, quinolones, fluoroquinolnes, macrolideantibiotics, peptide antibiotics, cyclosporines, erythromycin,clindamycin, and combinations thereof.

The composition may include a topical anesthetic. The topical anestheticcan be of any type. Examples of topical anesthetics include, but are notlimited to, benzocaine, lidocaine, bupivacaine, chlorprocaine,dibucaine, etidocaine, mepivacaine, tetracaine, dyclonine, hexylcaine,procaine, cocaine, ketamine, pramoxine, phenol, pharmaceuticallyacceptable salts thereof, and combinations thereof.

The composition may include an anti-viral agent. The anti-viral agentcan be of any type. Examples of anti-viral agents include, but are notlimited to, proteins, polypeptides, peptides, fusion protein antibodies,nucleic acid molecules, organic molecules, inorganic molecules, andsmall molecules that inhibit or reduce the attachment of a virus to itsreceptor, the internalization of a virus into a cell, the replication ofa virus, or release of virus from a cell. In particular, anti-viralagents include, but are not limited to, nucleoside analogs (e.g.zidovudine, acyclovir, acyclovir prodrugs, famciclovir, gangcyclovir,vidarabine, idoxuridine, trifluridine, and ribavirin), n-docosanollfoscarnet, amantadine, rimantadine, saquinavir, indinavir, ritonavir,idoxuridine alpha-interferons and other interferons, AZT, andcombinations thereof.

Additional examples of actives include analgesic agents andantihypertensive agents. Analgesic agents are known in the art and arecolloquially referred to as painkillers. The analgesic agent may beselected from any known analgesic agents, and specific examples thereofinclude paracetamol (acetaminophen), morphine, codeine, heroine,methadone, thebaine, orpiarine, buprenorphine, morphinans,benzomorphans, acetaminophen, butorphanol, diflunisal, fenoprofen,fentanyl, fentanyl citrate, hydrocodone, aspirin, sodium salicylate,ibuprofen, oxymorphone, pentaxicine, naproxen, nalbuphine, mefenamicacid, meperidine and dihydroergotamine, non-steroidal anti-inflammatoryagents, such as salicylates, and opioid agents, such as morphine andoxycodone. Antihypertensive agents are known in the art for treating orreducing hypertension, i.e., high blood pressure. The antihypertensiveagent may be selected from any known antihypertensive agents, andspecific examples thereof include diuretics, adrenergic receptorantagonists (e.g. beta blockers), benzodiazepines, calcium channelblockers, renin inhibitors, etc.

A typical narcotic antagonist is haloxone. Exemplary antitussive agentsinclude, without limitation, diphenhydramine, guaifenesin,hydromorphone, ephedrine, phenylpropanolamine, theophylline, codeine,noscapine, levopropoxyphene, carbetapentane, chlorpehndianol andbenzonatate.

Among the sedatives which may be utilized are, without limitation,chloral hydrate, butabarbital, alprazolam, amobarbital,chlordiazepoxide, diazepam, mephobarbital, secobarbital,diphenhydramine, ethinamate, flurazepam, halazepam, haloperidol,prochlorperazine, oxazepam, and talbutal.

Examples of cardiac drugs are, without limitation, quinidine,propranolol, nifedipine, procaine, dobutamine, digitoxin, phenyloin,sodium nitroprusside, nitroglycerin, verapamil HCl, digoxin, nicardipineHCl, and isosorbide dinitrate.

Antiemetics are illustrated by, without limitation, thiethylperazine,metoclopramide, cyclizine, meclizine, prochlorperazine, doxylaminesuccinate, promethazine, triflupromazine, and hydroxyzine.

A typical dopamine receptor agonist is bromocriptine mesylate. Exemplaryamino acid, peptide and protein hormones include, without limitation,thyroxine, growth hormone (GH), interstitial cell stimulating hormone(ICSH), follicle-stimulating hormone (FSH), thyrotropic hormone (TSH),adrenocorticotropic hormone (ACTH), gonadotropin releasing hormone(GnRH) such as leuprolide acetate, vasopressin and their activedegradation products Some products may have sufficiently high molecularweights that absorption through the stratum corneum or mucous membranesmay be difficult. Therefore, the invention is applicable only to thosehormones which have molecular weights and stereo configurations whichwill allow passage through the skin.

Female sex hormones that can be used include, without limitations,estradiol, diethylstilbestrol, conjugated estrogens, estrone,norethindrone, medroxyprogesterone, progesterone, and norgestrel.Typical male sex hormones that may be utilized may be represented by,without limitation, testosterone, methyltestosterone, andfluoxymesterone.

As introduced above, the emulsion may include various additives (e.g.those added during preparation of the emulsion), such that the emulsionitself functions as an end-use composition. However, the emulsion mayalso be combined with various additional components (e.g. after itspreparation), such as those described above, and thus formulated intovarious end-use compositions, such as a personal care compositions. Suchcompositions may be of any form, such as a cream, gel, powder, paste, orfreely pourable liquid. Compositions comprising or formed from theemulsion of the present disclosure may exhibit improved application andcosmetic properties (including reduced tackiness and stickiness), andimproved clarity/low residue properties.

In some embodiments, the emulsion is itself a personal care composition,or may be formulated into a personal care composition. In suchembodiments, the personal care composition may be formulated to becosmetic, therapeutic, functional with respect to a portion of a body towhich the personal care composition is applied, or some combinationsthereof. Examples of personal care compositions include antiperspirantsand deodorants, skin care creams, skin care lotions, moisturizers,facial treatments (e.g. acne or wrinkle removers), personal and facialcleansers, bath oils, perfumes, colognes, sachets, sunscreens, pre-shaveand after-shave lotions, shaving soaps and lathers, shampoos,conditioners, hair colorants, hair relaxants, hair sprays, mousses, hairgels, permanents, depilatories, cuticle coats, make-ups, colorcosmetics, foundations, concealers, blushes, lipsticks, eyeliners,mascara, oil removers, color cosmetic removers, and medicament creams,pastes or sprays (e.g. for anti-acnes, dental hygienics, antibiotics,healing promotives, etc.). In general, the personal care compositioncomprising the emulsion is formulated with a carrier that permitsapplication in a conventional form, such as a liquid, rinse, lotion,cream, paste, gel, foam, mousse, ointment, spray, aerosol, soap, stick,soft solid, or solid gel, e.g. depending on the intended use. Whatconstitutes a suitable carrier for formulating the personal carecomposition is readily apparent to one of ordinary skill in the art, andmay be selected from those carriers exemplified herein.

The personal care composition may be in any form, either liquid ornon-liquid (semi-solid, soft solid, solid, etc.). For example, thepersonal care composition may be a paste, a solid, a gel, or a cream.Additionally, regardless of how the emulsion was prepared, the personalcare composition formed from the emulsion may itself be an emulsion,such as an oil-in-water or water-in-oil emulsion, a multiple emulsion,such as an oil-in-water-in-oil emulsion or a water-in-oil-in-wateremulsion, or a solid, rigid or supple gel, including anhydrous gels. Thepersonal care composition can also be in a form chosen from atranslucent anhydrous gel and a transparent anhydrous gel. The personalcare composition may, for example, comprise an external or continuousfatty phase. The personal care composition may be anhydrous. In someinstances, the personal care composition can be a molded composition orcast as a stick or a dish. In specific embodiments, the personal carecomposition comprising the emulsion is a molded poured stick. In suchembodiments, the personal care composition (e.g. in stick form) maybehave as deformable, flexible elastic solid, having increased elasticsoftness on application.

The personal care composition comprising the emulsion can be used by anymethod, such as via application to a human body (e.g. skin or hair) byhand or with an applicator (e.g. a brush or sprayer). In someembodiments, the personal care composition may be intended to be removedafter such application, e.g. by washing, wiping, peeling, and the like,or combinations thereof.

As mentioned above, the copolymer in general, and specific embodimentsof acrylic copolymers in particular, have excellent utility whenutilized in or applied as a cosmetic ingredient or film-forming agent,including for quasi-drug formulations or topical formulations. Thoughnot limited to this particular end use application, the inventivecopolymer can be utilized instead of or in combination with anyconventional copolymer having a carbosiloxane dendrimer structure, whichare ubiquitous in existing cosmetic formulations.

For example, the copolymer can partially or fully replace a siliconeacrylate copolymer having a carbosiloxane dendrimer structure (e.g.conventional product of FA4001 CM Silicone Acrylate, FA4002 ID SiliconeAcrylate, FA4003 silicone Acrylate etc.) in cosmetic formulations infollowing patent application publications: WO2012/143344, WO2014/154701,WO2014/154700, WO2015/092632, WO2015/097110, WO2015/097103,WO2017/050699, WO2017/050922, WO2010/026538, WO2014/087183,WO2011/051323, JP2007-320960, WO2016/030842, JP2010-018612,JP2011-016734, JP2011-016732, JP2011-016733, JP2011-016734, JP2011-126807, JP 2011-126808, JP2013-001672, JP 2014-034568, JP2014-040388, JP 2014-227358, JP2015-098451, JP 2015-137252, JP2016-008200, JP2016-088848, JP 2016-121095, JP 2016-160191, JP2018-090495, JP2000-072784, JP07-309714, JP2007-320960, JP2014-040512,WO2017/061090, JP2011-149017, JP2014-040512, JP2014-040511,WO/2018/086139, WO/2018/186138, PCT/JP18/022412, and PCT/JP18/022413.

Specific intended end use applications of the inventive copolymer arebased on the cosmetic formulations of the above patent applicationpublications, whereby a conventional copolymer having a carbosiloxanedendrimer structure of these patent application publications is replacedwith the inventive copolymer of this disclosure. In certain embodiments,the inventive copolymer is utilized in combination with the conventionalcopolymer having the carbosiloxane dendrimer structure. In otherembodiments, the inventive copolymer is utilized in lieu of (and toreplace) the conventional copolymer having the carbosiloxane dendrimerstructure.

Furthermore, emulsion compositions comprising copolymers can bepartially or fully replaced with the inventive copolymer in emulsion.For example, copolymer emulsions in cosmetic formulations disclosed inthe following documents can be replaced with emulsions comprising theinventive copolymers: WO2017/061090, WO/2018/086139, WO/2018/186138,PCT/JP18/022412, PCT/JP18/022413 and Research Disclosures: No.IPCOM000243971 D, and No. IPCOM0002457480.

By replacing conventional silicone acrylate co-polymer havingcarbosiloxane dendrimer structure with the copolymer comprising thebranched organosilicon moiety in available and conventional cosmeticformulations, the skilled person in the art can anticipate and designsimilar or improved cosmetic formulation using the copolymer comprisingthe branched organosilicon moiety.

The following examples, illustrating embodiments of this disclosure, areintended to illustrate and not to limit the invention. The brief summaryimmediately below provides information as to certain abbreviations,shorthand notations, and components utilized in the Examples. Each groupnot expressly shown and pending from a silicon atom is a methyl group(—CH₃) unless otherwise indicated.

“Si10Vi” is a branched organosilicon having 10 silicon atoms, a vinylgroup (Vi; —CH═CH₂), and is of the general formula (a) below. “Si7Vi” isa branched organosilicon having 7 silicon atoms, a vinyl group, and isof the general formula (b) below.

In formulae (a) and (b) above, R is a methyl group and R⁷ is a vinylgroup.

“Si10H” is similar to formula (a) above, but R⁷ is H. Likewise, “Si7H”is similar to formula (b) above, but R⁷ is H.

“ETM (converter)” is of the general formula (c) below. “EHM (converter)”is of the general formula (d) below.

In formulae (c) and (d) above, each R is a methyl group, each D¹ is—CH₂—CH₂—, and R′ is a propyl group (—CH₂—CH₂—CH₃). The ETM (converter)can also be referred to astrimethoxysilylethyl-1,1,3,3-tetramethyldisiloxane.

“Pt” is platinum (catalyst). “Karstedt's catalyst” is a Pt divinyltetramethyl disiloxane complex containing about 2 wt. % of Pt in asolvent (e.g. xylenes). Karstedt's catalyst is described in U.S. Pat.Nos. 3,715,334 and 3,814,730. “Rh catalyst” is RhCODCl dimer (0.01 M intoluene), which may also be referred to aschloro(1,5-cyclooctadiene)rhodium(I) dimer.

“Si12H” is of the general formula (e) below:

The Si12H can be prepared by the hydrosilylation reaction of Si10Vi and1,1,3,3-tetramethyldisiloxane in the presence of Pt.

“Allyl glycidyl ether (converter)” is of the general formula (f) below:

The allyl glycidyl ether (converter) can be prepared by thehydrosilylation reaction of allyl glycidyl ether and1,1,3,3-tetramethyldisiloxane (HSi(CH₃)₂—O—Si(CH₃)₂H) in the presence ofPt.

Example 1: Synthesis of Si12(OMe)₃

66.1 g of Si10Vi and 25.4 g of ETM (converter) were mixed in a 250 mLflask to form a mixture. The flask is equipped with a mechanicalstirrer, a thermal couple, and a water-cooled condenser adapted to anitrogen (N₂) bubbler. The mixture was heated to 40-50° C. and then 10ppm of Pt was added to form a catalyzed mixture. No exotherm wasobserved.

The catalyzed mixture was heated to 80° C. for 3 hours and 40 minutes toform a reaction mixture. The reaction mixture was then cooled to 58° C.Next, 5 g of activated carbon was added to the reaction mixture,followed by stirring for 3 hours and then filtering through a 0.45 μmmembrane to remove Pt. After filtering, volatiles were removed via arotary evaporator (“rotovap”) at 100° C. and <1 mmHg for 40 minutes.

The reaction product formed in this example comprises a branchedorganosilicon compound of the general formula below:

where X is —(CH₂)₂—; Y is

and each of R and D¹ is as defined above. This compound provides methoxygroups.

Example 2: Synthesis of Si16(OMe)₆

51.4 g of Si10Vi and 42.5 g of EHM (converter) were mixed in a 250 mLflask to form a mixture. The flask is equipped as in Example 1. Themixture is heated to 45° C. and then 10 ppm of Pt was added to form acatalyzed mixture. No exotherm was observed

The catalyzed mixture was heated to 98-100° C. for ˜12 hours, with anadditional 10 ppm of Pt added at ˜4 hours and at 8 hours to form areaction mixture. The reaction mixture was then cooled to 70° C. Next,9.7 g of activated carbon was added to the reaction mixture, followed bystirring for 3.5 hours and then filtering through a 0.45 μm membrane toremove Pt. After filtering, volatiles were removed via rotovap at 120°C. and <1 mmHg for 40 minutes.

The reaction product formed in this example comprises a branchedorganosilicon compound of the general formula below:

where X is —(CH₂)₂—; Y is

and each of R, R′ and D¹ is as defined above. This compound providesmethoxy groups.

Example 3: Synthesis of Si9EP

5 g of Si7Vi, 2.28 g allyl glycidyl ether (converter) and 10 μL ofKarstedt's catalyst was added to a 40 mL scintillation vial to form areaction mixture. The reaction mixture was heated to 50° C. andmaintained for 16 hours. No purification was done.

The reaction product formed in this example comprises a branchedorganosilicon compound of the general formula below:

where R is as defined above; X is —(CH₂)₂—; and Y is

where the left silicon atom is dimethyl substituted and includes acovalent bond to a carbon atom of X. This compound provides an epoxygroup.

Example 4: Synthesis of Si12EP

6 g of Si12H and 20 mL of toluene are added to a 20 mL 1-neck flaskreactor to form a mixture. The reactor was purged with nitrogen and thencapped with a septum having a thermocouple going through it. The mixturewas heated to 50° C. and then 20 μL of Rh catalyst was added to form acatalyzed mixture.

Next, an excess amount of allyl glycidyl ether (2 g) was added as a shotto form a reaction mixture. A 5° C. exotherm was observed over a 30minute period. After 30 minutes, the excess allyl glycidyl ether andtoluene were stripped off at 75 mTorr and 25° C. The material was thencharacterized by NMR.

The reaction product formed in this example comprises a branchedorganosilicon compound of the general formula below:

where X is —(CH₂)₂—; and Y is

where the left silicon atom is dimethyl substituted and includes acovalent bond to a carbon atom of X. This compound provides an epoxygroup.

Example 5: Synthesis of Si12EP

10 g of Si10Vi and 20 mL of toluene was added to a 250 mL 2-neck roundbottom flask to form a mixture. One port was plugged with a septumhaving a thermocouple going through it and an addition funnel with 2.81g of allyl glycidyl ether (converter) was placed in the other port. Themixture was heated to 50° C. and then 10 μL of Karstedt's catalyst wasadded to form a catalyzed mixture.

Next, addition of the converter was started to form a reaction mixture.The reaction mixture was maintained between 50-55° C. for 30 minutes.The toluene was then stripped off at 75 mTorr and 25° C. The materialwas then characterized by NMR.

The reaction product formed in this example comprises a branchedorganosilicon compound of the general formula illustrated in Example 4above. The branched organosilicon compound is also illustrated by theformula below:

Example 6: Synthesis of Si110C

5.02 g of Si10Vi, 724 μL of dimethylchlorosilane (Cl(CH₃)₂SiH) and 30 μLof Karstedt's catalyst was added to a 40 mL scintillation vial to form areaction mixture. The reaction mixture was heated at 50° C. for 24 hoursand then cooled to room temperature (˜23° C.). Next, excessdimethylchlorosilane was stripped at 75 mTorr and 25° C. The materialwas then characterized by NMR.

The reaction product formed in this example comprises a branchedorganosilicon compound (“Si11Cl”) of the formula below:

Example 7: Synthesis of Si13MA

A solution of 2.38 g of Si11Cl from Example 6 and 2 mL oftetrahydrofuran (THF) is prepared. Separately, 0.841 g of converter(below) and 578 μL of trimethylamine (“NEt₃”) was added to a 40 mLscintillation vial to form a mixture.

The solution was slowly added to the mixture at room temperature (˜23°C.) to form a reaction mixture. The reaction mixture was stirred at roomtemperature for 22 hours. Next, hexane was used forfiltering/precipitating salt from the reaction mixture. Solvent was thenstripped from the reaction mixture, and spectral data was collected.

Converter has the following structure:

The reaction product formed in this example comprises a branchedorganosilicon compound of the general formula below:

This compound provides a methacrylate group.

Example 8: Synthesis of Si12MA

21 g (˜20 eq.) of allyl methacrylate was added to a 250 mL 2-neck roundbottom flask. One port was plugged with a septum having a thermocouplegoing through it and an addition funnel with 5 g of Si12H was placed inthe other port. The allyl methacrylate was heated to 50° C. and then 10μL of Karstedt's catalyst was added to form a catalyzed mixture.

Next, addition of the Si12H was started to form a reaction mixture. Thereaction mixture was maintained at 50° C. for 30 minutes. The excessallyl methacrylate then was stripped off at 75 mTorr and 25° C. Thematerial was then characterized by NMR.

The reaction product formed in this example comprises a branchedorganosilicon compound of the general formula below:

where X is —(CH₂)₂—; and Y is

where the left silicon atom is dimethyl substituted and includes acovalent bond to a carbon atom of X. This compound provides amethacrylate group.

Example 9: Synthesis of Si9MA

5 g of Si7Vi, 2.39 g of allyl methacrylate (converter) and 10 μL ofKarstedt's catalyst was added to a 40 mL scintillation vial to form areaction mixture. The reaction mixture was heated to 50° C. andmaintained for 16 hours. No purification was done.

The reaction product formed in this example comprises a branchedorganosilicon compound of the general formula below:

where R is as defined above; X is —(CH₂)₂—; and Y is

where the left silicon atom is dimethyl substituted and includes acovalent bond to a carbon atom of X. This compound provides amethacrylate group.

The terms “comprising” or “comprise” are used herein in their broadestsense to mean and encompass the notions of “including,” “include,”“consist(ing) essentially of,” and “consist(ing) of. The use of “forexample,” “e.g.,” “such as,” and “including” to list illustrativeexamples does not limit to only the listed examples. Thus, “for example”or “such as” means “for example, but not limited to” or “such as, butnot limited to” and encompasses other similar or equivalent examples.The term “about” as used herein serves to reasonably encompass ordescribe minor variations in numerical values measured by instrumentalanalysis or as a result of sample handling. Such minor variations may bein the order of ±0-25, ±0-10, ±0-5, or ±0-2.5, % of the numericalvalues. Further, The term “about” applies to both numerical values whenassociated with a range of values. Moreover, the term “about” may applyto numerical values even when not explicitly stated.

Generally, as used herein a hyphen “-” or dash “-” in a range of valuesis “to” or “through”; a “>” is “above” or “greater-than”; a “≥” is “atleast” or “greater-than or equal to”; a “<” is “below” or “less-than”;and a “≤” is “at most” or “less-than or equal to.” On an individualbasis, each of the aforementioned applications for patent, patents,and/or patent application publications, is expressly incorporated hereinby reference in its entirety in one or more non-limiting embodiments.

It is to be understood that the appended claims are not limited toexpress and particular compounds, compositions, or methods described inthe detailed description, which may vary between particular embodimentswhich fall within the scope of the appended claims. With respect to anyMarkush groups relied upon herein for describing particular features oraspects of various embodiments, different, special, and/or unexpectedresults may be obtained from each member of the respective Markush groupindependent from all other Markush members. Each member of a Markushgroup may be relied upon individually and or in combination and providesadequate support for specific embodiments within the scope of theappended claims.

Further, any ranges and subranges relied upon in describing variousembodiments of the present invention independently and collectively fallwithin the scope of the appended claims, and are understood to describeand contemplate all ranges including whole and/or fractional valuestherein, even if such values are not expressly written herein. One ofskill in the art readily recognizes that the enumerated ranges andsubranges sufficiently describe and enable various embodiments of thepresent invention, and such ranges and subranges may be furtherdelineated into relevant halves, thirds, quarters, fifths, and so on. Asjust one example, a range “of from 0.1 to 0.9” may be further delineatedinto a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, whichindividually and collectively are within the scope of the appendedclaims, and may be relied upon individually and/or collectively andprovide adequate support for specific embodiments within the scope ofthe appended claims. In addition, with respect to the language whichdefines or modifies a range, such as “at least,” “greater than,” “lessthan,” “no more than,” and the like, it is to be understood that suchlanguage includes subranges and/or an upper or lower limit. As anotherexample, a range of “at least 10” inherently includes a subrange of fromat least 10 to 35, a subrange of from at least 10 to 25, a subrange offrom 25 to 35, and so on, and each subrange may be relied uponindividually and/or collectively and provides adequate support forspecific embodiments within the scope of the appended claims. Finally,an individual number within a disclosed range may be relied upon andprovides adequate support for specific embodiments within the scope ofthe appended claims. For example, a range “of from 1 to 9” includesvarious individual integers, such as 3, as well as individual numbersincluding a decimal point (or fraction), such as 4.1, which may berelied upon and provide adequate support for specific embodiments withinthe scope of the appended claims.

The invention has been described in an illustrative manner, and it is tobe understood that the terminology which has been used is intended to bein the nature of words of description rather than of limitation.Obviously, many modifications and variations of the present inventionare possible in light of the above teachings. The invention may bepracticed otherwise than as specifically described.

1. A branched organosilicon compound having the following generalformula:

where each R¹ is selected from R and —OSi(R⁴)₃, with the proviso that atleast one R¹ is —OSi(R⁴)₃; where each R⁴ is selected from R, —OSi(R⁵)₃,and —[OSiR₂]_(m)OSiR₃, where 0≤m≤100; where each R⁵ is selected from R,—OSi(R⁶)₃, and —[OSiR₂]_(m)OSiR₃, where m is defined above; where eachR⁶ is selected from R and —[OSiR₂]_(m)OSiR₃, where m is defined above;with the proviso that at least one of R⁴, R⁵ and R⁶ is—[OSiR₂]_(m)OSiR₃, where m is defined above; X is a divalent linkinggroup; and Y is selected from one of formulas (I)-(III):

where each R is an independently selected substituted or unsubstitutedhydrocarbyl group; each D¹ is an independently selected divalenthydrocarbon group; each subscript a is independently 0 or 1; eachsubscript b is independently 0 or 1; each subscript e is independently 1or 2; each subscript f is independently 0 or 1, with the proviso thatwhen f is 1, b is 1; subscript t is ≥0; subscript u is >0; 0≤n≤10; andR³ comprises a halogen atom, an acryloxy functional moiety, analkoxysilyl functional moiety, or an epoxy functional moiety.
 2. Thebranched organosilicon compound of claim 1, wherein each R¹ is—OSi(R⁴)₃, and wherein at least one of R⁴ is —[OSiR₂]_(m)OSiR₃, where Rand m are defined above.
 3. The branched organosilicon compound of claim1, having the following general formula:

where R is independently selected and defined above, and each R⁵ isindependently selected and defined above, and X and Y are defined above.4. The branched organosilicon compound of claim 1, having the followinggeneral formula:

where R is independently selected and defined above, each R⁵ isindependently selected and defined above, and X and Y are defined above.5. The branched organosilicon compound of claim 1, having the followinggeneral formula:

where R is independently selected and defined above, each R⁵ isindependently selected and defined above, and X and Y are defined above.6. The branched organosilicon compound of claim 1, wherein: (i) X is adivalent hydrocarbon group; (ii) m is 0 or 1; (iii) each R is methyl; or(iv) any combination of (i)-(iii).
 7. A method of preparing a branchedorganosilicon compound, said method comprising: reacting anorganosilicon compound and a functional compound in the presence of ahydrosilylation catalyst to give the branched organosilicon compound;wherein the organosilicon compound includes one of a silicon-bondedhydrogen atom and a silicon-bonded ethylenically unsaturated group, withthe proviso that when the organosilicon compound includes asilicon-bonded hydrogen atom, the functional compound includes anethylenically unsaturated group, and when the organosilicon compoundincludes a silicon-bonded ethylenically unsaturated group, thefunctional compound includes a silicon-bonded hydrogen atom; and whereinthe branched organosilicon compound is the branched organosiliconcompound of claim
 1. 8. The method of claim 7, wherein the organosiliconcompound has the following general formula:

where X is a divalent linking group; each R is independently asubstituted or unsubstituted hydrocarbyl group; 0≤n≤10; each R¹ isselected from R and —OSi(R⁴)₃, with the proviso that at least one R¹ is—OSi(R⁴)₃; where each R⁴ is selected from R, —OSi(R⁵)₃, and—[OSiR₂]_(m)OSiR₃, where 0≤m≤100; where each R⁵ is selected from R,—OSi(R⁶)₃, and —[OSiR₂]_(m)OSiR₃, where m is defined above; where eachR⁶ is selected from R and —[OSiR₂]_(m)OSiR₃, where m is defined above;with the proviso that at least one of R⁴, R⁵ and R⁶ is—[OSiR₂]_(m)OSiR₃, where m is defined above; and where R⁷ is H orcomprises a silicon-bonded hydrogen atom or an ethylenically unsaturatedgroup
 9. The method of claim 7, wherein the functional compound includesa halogen atom, an acryloxy functional moiety, an alkoxysilyl functionalmoiety, or an epoxy functional moiety.
 10. The method of claim 8,wherein R⁷ comprises an ethylenically unsaturated group, and wherein thefunctional compound has one of the following general formulas (VI) and(VII):

where each R is an independently selected substituted or unsubstitutedhydrocarbyl group; each D¹ is an independently selected divalenthydrocarbon group; each subscript a is independently 0 or 1; eachsubscript b is independently 0 or 1; each subscript e is independently 1or 2; each subscript f is independently 0 or 1, with the proviso thatwhen f is 1, b is 1; subscript t is ≥0; and subscript u is >0.
 11. Acopolymer comprising the reaction product of a branched organosiliconcompound and a second compound reactive with the branched organosiliconcompound; wherein the branched organosilicon compound is the branchedorganosilicon compound of claim
 1. 12. A method of preparing acopolymer, said method comprising reacting a branched organosiliconcompound and a second compound reactive with the branched organosiliconcompound to give the copolymer; wherein the copolymer is the copolymerof claim
 11. 13. A composition comprising the branched organosiliconcompound of claim
 1. 14. The composition of claim 13, further defined asat least one of: (i) an emulsion; (ii) an aqueous composition; (iii) asurfactant composition; (iv) a wetting composition; (v) an aqueousfilm-forming foam; (vi) a surface tension modifier; (vii) anantiblocking additive; (viii) an agricultural composition; (ix) acoating composition; (x) a paint composition; (xi) a surface treatingcomposition; (xii) a film-forming composition; and (xiii) a cosmeticcomposition.
 15. A composition comprising the copolymer of claim
 11. 16.(canceled)